Ethylene oligomerization processes

ABSTRACT

Disclosed herein is a process for forming an oligomer product comprising (a) introducing into a reaction zone (i) ethylene; (ii) a heteroatomic ligand metal salt complex comprising a heteroatomic ligand complexed to a first metal salt; (iii) a second metal salt wherein an equivalent molar ratio of the second metal salt to the heteroatomic ligand of the heteroatomic ligand metal salt complex is at least 0.5:1 and where the second metal salt is an iron salt, a cobalt salt, or any combination thereof; (iv) an organoaluminum compound; and (b) forming an oligomer product. Also disclosed herein is a process comprising (a) introducing into a reaction zone (i) ethylene; (ii) a heteroatomic ligand; (iii) a metal salt where an equivalent molar ratio of the metal salt to the heteroatomic ligand is at least 1.5:1; (iv) an organoaluminum compound; and (b) forming an oligomer product.

CROSS-REFERENCE TO RELATED APPLICATIONS

Not applicable.

FIELD

The present disclosure relates to processes for producing alpha olefins.More particularly, the present disclosure relates to improved processesfor oligomerizing ethylene.

BACKGROUND

Alpha olefins are important items of commerce. Their many applicationsinclude employment as intermediates in the manufacture of detergents, asprecursors to more environmentally friendly refined oils, as monomers,and as precursors for many other types of products. One method of makingalpha olefins is via oligomerization of ethylene in a catalytic reactioninvolving various types of catalysts and/or catalyst systems. Examplesof catalysts and catalyst systems used commercially in theoligomerization of ethylene include alkylaluminum compounds, certainnickel-phosphine complexes, a titanium halide with a Lewis acid (e.g.,diethylaluminum chloride), a selective 1-hexene catalyst systemcontaining a chromium containing compound (e.g., a chromiumcarboxylate), a nitrogen containing ligand (e.g., a pyrrole) and a metalalkyl (e.g., alkylaluminum compounds), and a selective trimerizationand/or tetramerization catalyst system using a metal complex of acompound having a diphosphinylaminyl group.

Several oligomerization catalyst systems to produce alpha olefins arebased upon metal complexes of pyridine bis-imines and metal complexes ofα-diimine compounds having a metal complexing group, among others. Thesecatalyst systems typically use an organoaluminum compound (e.g.,aluminoxane) as a component of the catalyst system for olefinoligomerization.

Applications and demand for olefins (e.g., alpha olefins) continue tomultiply and competition to supply them correspondingly intensifies.Thus, additional novel and improved catalyst systems and processes forolefin oligomerization are desirable.

SUMMARY

Disclosed herein is a process for forming an oligomer product comprising(a) introducing into a reaction zone (i) ethylene; (ii) a heteroatomicligand metal salt complex comprising a heteroatomic ligand complexed toa first metal salt where the first metal salt is an iron salt, a cobaltsalt, or a combination thereof; (iii) a second metal salt wherein anequivalent molar ratio of the second metal salt to the heteroatomicligand of the heteroatomic ligand metal salt complex is at least 0.5:1and where the second metal salt is an iron salt, a cobalt salt, or anycombination thereof; (iv) an organoaluminum compound; (v) optionallyhydrogen; and (vi) optionally an organic reaction medium; and (b)forming an oligomer product in the reaction zone.

Also disclosed herein is a process for forming an oligomer productcomprising (a) introducing into a reaction zone (i) ethylene; (ii)heteroatomic ligand; (iii) a metal salt where (1) the metal salt is aniron salt, a cobalt salt, or any combination thereof, and (2) anequivalent molar ratio of the metal salt to the heteroatomic ligand isat least 1.5:1; (iv) an organoaluminum compound; (v) optionallyhydrogen; and (vi) optionally an organic reaction medium; and (b)forming an oligomer product in the reaction zone.

BRIEF DESCRIPTION OF DRAWINGS

Not applicable.

DETAILED DESCRIPTION

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Groups of elements of the periodic table are indicated using thenumbering scheme found in the version of the periodic table of elementspublished in Chemical and Engineering News, 63(5), 27, 1985. In someinstances, a group of elements can be indicated using a common nameassigned to the group; for example alkali metals for Group 1 elements,alkaline earth metals for Group 2 elements, transition metals for Group3-12 elements, and halogens for Group 17 elements, among others.

Regarding claim transitional terms or phrases, the transitional term“comprising”, which is synonymous with “including,” “containing,”“having,” or “characterized by,” is inclusive or open-ended and does notexclude additional, unrecited elements or method steps. The transitionalphrase “consisting of” excludes any element, step, or ingredient notspecified in the claim. The transitional phrase “consisting essentiallyof” limits the scope of a claim to the specified materials or steps andthose that do not materially affect the basic and novelcharacteristic(s) of the claimed invention. A “consisting essentiallyof” claim occupies a middle ground between closed claims that arewritten in a “consisting of” format and fully open claims that aredrafted in a “comprising” format. Absent an indication to the contrary,when describing a compound or composition “consisting essentially of” isnot to be construed as “comprising,” but is intended to describe therecited component that includes materials which do not significantlyalter the composition or method to which the term is applied. Forexample, a feedstock consisting essentially of a material A can includeimpurities typically present in a commercially produced or commerciallyavailable sample of the recited compound or composition. When a claimincludes different features and/or feature classes (for example, amethod step, feedstock features, and/or product features, among otherpossibilities), the transitional terms “comprising,” “consistingessentially of,” and “consisting of” apply only to the feature classwhich is utilized and it is possible to have different transitionalterms or phrases utilized with different features within a claim. Forexample, a method can comprise several recited steps (and othernon-recited steps) but utilize a catalyst system preparation consistingof specific or alternatively, consist of specific steps and/or utilize acatalyst system comprising recited components and other non-recitedcomponents.

Within this specification, use of“comprising” or an equivalentexpression contemplates the use of the phrase “consisting essentiallyof,” “consists essentially of,” or equivalent expressions as alternativeembodiments to the open-ended expression. Additionally, use of“comprising” or an equivalent expression or use of “consistingessentially of” in the specification contemplates the use of the phrase“consisting of,” “consists of,” or equivalent expressions as analternative to the open-ended expression or middle ground expression,respectively. For example, “comprising” should be understood to include“consisting essentially of,” and “consisting of” as alternativeembodiments for the aspect, features, and/or elements presented in thespecification unless specifically indicated otherwise.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps.

In the specification and claims, the terms “a,” “an,” and “the” areintended, unless specifically indicated otherwise, to include pluralalternatives, e.g., at least one, or one or more. For instance, thedisclosure of “a trialkylaluminum compound” is meant to encompass onetrialkylaluminum compound, or mixtures or combinations of more than onetrialkylaluminum compound unless otherwise specified.

In this disclosure, the terms first, second, and third, among others,can be utilized to differentiate multiple occurrences of a similarelement. For example, a method can utilize two or more solvents indifferent steps of a method, or alternatively, two different solvents ina mixture. The differentiating term can be applied to any elementdescribed herein when necessary to provide a differentiation. It shouldbe understood that the numerical or alphabetical precedence of thedifferentiating terms do not imply a particular order or preference ofthe element in a method or compound described herein unless specifiedotherwise.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to a C₆hydrocarbon refers to all hydrocarbon having 6 carbon atoms, a generalreference to pentane includes n-pentane, 2-methyl-butane, and2,2-dimethylpropane, and a general reference to a butyl group includesan n-butyl group, a sec-butyl group, an iso-butyl group, and atert-butyl group. Additionally, the reference to a general structure orname encompasses all enantiomers, diastereomers, and other opticalisomers whether in enantiomeric or racemic forms, as well as mixtures ofstereoisomers, as the context permits or requires. For any particularformula or name that is presented, any general formula or name presentedalso encompasses all conformational isomers, regioisomers, andstereoisomers that can arise from a particular set of substituents.

A chemical “group” is described according to how that group is formallyderived from a reference or “parent” compound, for example, by thenumber of hydrogen atoms formally removed from the parent compound togenerate the group, even if that group is not literally synthesized inthis manner. These groups can be utilized as substituents or coordinatedor bonded to metal atoms. By way of example, an “alkyl group” formallycan be derived by removing one hydrogen atom from an alkane, while an“alkylene group” formally can be derived by removing two hydrogen atomsfrom an alkane. Moreover, a more general term can be used to encompass avariety of groups that formally are derived by removing any number (“oneor more”) hydrogen atoms from a parent compound, which in this examplecan be described as an “alkane group,” and which encompasses an “alkylgroup,” an “alkylene group,” and materials have three or more hydrogensatoms, as necessary for the situation, removed from the alkane.Throughout, the disclosure that a substituent, ligand, or other chemicalmoiety can constitute a particular “group” implies that the well-knownrules of chemical structure and bonding are followed when that group isemployed as described. When describing a group as being “derived by,”“derived from,” “formed by,” or “formed from,” such terms are used in aformal sense and are not intended to reflect any specific syntheticmethods or procedure, unless specified otherwise or the context requiresotherwise.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe any non-hydrogen moiety that formally replaces a hydrogen inthat group, and is intended to be non-limiting. A group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.“Substituted” is intended to be non-limiting and include inorganicsubstituents or organic substituents.

The term “organyl group” is used herein in accordance with thedefinition specified by IUPAC: an organic substituent group, regardlessof functional type, having one free valence at a carbon atom. Similarly,an “organylene group” refers to an organic group, regardless offunctional type, derived by removing two hydrogen atoms from an organiccompound, either two hydrogen atoms from one carbon atom or one hydrogenatom from each of two different carbon atoms. An “organic group” refersto a generalized group formed by removing one or more hydrogen atomsfrom carbon atoms of an organic compound. Thus, an “organyl group,” an“organylene group,” and an “organic group” can contain organicfunctional group(s) and/or atom(s) other than carbon and hydrogen, thatis, an organic group can comprise functional groups and/or atoms inaddition to carbon and hydrogen. For instance, non-limiting examples ofatoms other than carbon and hydrogen include halogens, oxygen, nitrogen,phosphorus, and the like. Non-limiting examples of functional groupsinclude ethers, aldehydes, ketones, esters, sulfides, amines,phosphines, and so forth.

For the purposes of this application, the term or variations of the term“organyl group consisting essentially of inert functional groups” refersto an organyl group (having a free valence on a carbon atom) wherein theorganic functional group(s) and/or atom(s) other than carbon andhydrogen present in the functional group are restricted to thosefunctional group(s) and/or atom(s) other than carbon and hydrogen whichdo not complex with a metal compound and/or are inert under the processconditions defined herein. Thus, the term or variation of the term“organyl group consisting essentially of inert functional groups”further defines the particular organyl groups that can be present withinthe organyl group consisting essentially of inert functional groups.Additionally, the term “organyl group consisting essentially of inertfunctional groups” can refer to the presence of one or more inertfunctional groups within the organyl group. The term or variation of theterm “organyl group consisting essentially of inert functional groups”includes the hydrocarbyl group as a member (among other groups).Similarly, an “organylene group consisting essentially of inertfunctional groups” refers to an organic group formed by removing twohydrogen atoms from one or two carbon atoms of an organic compoundconsisting of inert functional groups and an “organic group consistingessentially of inert functional groups” refers to a generalized organicgroup consisting essentially of inert functional groups formed byremoving one or more hydrogen atoms from one or more carbon atoms of anorganic compound consisting of inert functional groups.

For purposes of this application, an “inert functional group” is a groupwhich does not substantially interfere with the process described hereinin which the material having an inert functional group takes part and/ordoes not complex with the metal compound of the metal complex. The term“does not complex with the metal compound” can include groups that couldcomplex with a metal compound but in particular molecules describedherein may not complex with a metal compound due to its positionalrelationship within a ligand. For example, while an ether group cancomplex with a metal compound, an ether group located at a para positionof a substituted phenyl phosphinyl group in an N²-phosphinyl amidine canbe an inert functional group because a single metal compound cannotcomplex with both the para ether group and the N²-phosphinyl amidinegroup of the same metal complex molecule. Thus, the inertness of aparticular functional group is not only related to the functionalgroup's inherent inability to complex the metal compound but can also berelated to the functional group's position within the metal complex.Non-limiting examples of inert functional groups which do notsubstantially interfere with processes described herein can include halo(fluoro, chloro, bromo, and iodo), nitro, hydrocarboxy groups (e.g.,alkoxy, and/or aroxy, among others), sulfidyl groups, and/or hydrocarbylgroups, among others.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thatthe presence of one or more halogen atoms replacing an equivalent numberof hydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” isused herein in accordance with the definition specified by IUPAC: aunivalent group formed by removing a hydrogen atom from a hydrocarbon.Similarly, a “hydrocarbylene group” refers to a group formed by removingtwo hydrogen atoms from a hydrocarbon, either two hydrogen atoms fromone carbon atom or one hydrogen atom from each of two different carbonatoms. Therefore, in accordance with the terminology used herein, a“hydrocarbon group” refers to a generalized group formed by removing oneor more hydrogen atoms (as necessary for the particular group) from ahydrocarbon. A “hydrocarbyl group,” “hydrocarbylene group,” and“hydrocarbon group” can be acyclic or cyclic groups, and/or can belinear or branched. A “hydrocarbyl group,” “hydrocarbylene group,” and“hydrocarbon group” can include rings, ring systems, aromatic rings, andaromatic ring systems, which contain only carbon and hydrogen.“Hydrocarbyl groups,” “hydrocarbylene groups,” and “hydrocarbon groups”include, by way of example, aryl, arylene, arene, alkyl, alkylene,alkane, cycloalkyl, cycloalkylene, cycloalkane, aralkyl, aralkylene, andaralkane groups, among other groups, as members.

The term “alkane” whenever used in this specification and claims refersto a saturated hydrocarbon compound. Other identifiers can be utilizedto indicate the presence of particular groups in the alkane (e.g.,halogenated alkane indicates that the presence of one or more halogenatoms replacing an equivalent number of hydrogen atoms in the alkane).The term “alkyl group” is used herein in accordance with the definitionspecified by IUPAC: a univalent group formed by removing a hydrogen atomfrom an alkane. Similarly, an “alkylene group” refers to a group formedby removing two hydrogen atoms from an alkane (either two hydrogen atomsfrom one carbon atom or one hydrogen atom from two different carbonatoms). An “alkane group” is a general term that refers to a groupformed by removing one or more hydrogen atoms (as necessary for theparticular group) from an alkane. An “alkyl group,” “alkylene group,”and “alkane group” can be acyclic or cyclic groups, and/or can be linearor branched unless otherwise specified. Primary, secondary, and tertiaryalkyl groups are derived by removal of a hydrogen atom from a primary,secondary, or tertiary carbon atom, respectively, of an alkane. Then-alkyl group can be derived by removal of a hydrogen atom from aterminal carbon atom of a linear alkane.

A cycloalkane is a saturated cyclic hydrocarbon, with or without sidechains, for example, cyclobutane. Unsaturated cyclic hydrocarbons havingone or more endocyclic double or one triple bond are called cycloalkenesand cycloalkynes, respectively. Cycloalkenes and cycloalkynes havingonly one, only two, only three, etc. . . . endocyclic double or triplebonds, respectively, can be identified by use of the term “mono,” “di,”“tri, etc. . . . within the name of the cycloalkene or cycloalkyne.Cycloalkenes and cycloalkynes can further identify the position of theendocyclic double or triple bonds.

A “cycloalkyl group” is a univalent group derived by removing a hydrogenatom from a ring carbon atom of a cycloalkane. For example, a1-methylcyclopropyl group and a 2-methylcyclopropyl group areillustrated as follows.

Similarly, a “cycloalkylene group” refers to a group derived by removingtwo hydrogen atoms from a cycloalkane, at least one of which is a ringcarbon. Thus, a “cycloalkylene group” includes both a group derived froma cycloalkane in which two hydrogen atoms are formally removed from thesame ring carbon, a group derived from a cycloalkane in which twohydrogen atoms are formally removed from two different ring carbons, anda group derived from a cycloalkane in which a first hydrogen atom isformally removed from a ring carbon and a second hydrogen atom isformally removed from a carbon atom that is not a ring carbon. A“cycloalkane group” refers to a generalized group formed by removing oneor more hydrogen atoms (as necessary for the particular group and atleast one of which is a ring carbon) from a cycloalkane. It should benoted that according to the definitions provided herein, generalcycloalkane groups (including cycloalkyl groups and cycloalkylenegroups) include those having zero, one, or more than one hydrocarbylsubstituent groups attached to a cycloalkane ring carbon atom (e.g., amethylcyclopropyl group) and is a member of the group of hydrocarbongroups. However, when referring to a cycloalkane group having aspecified number of cycloalkane ring carbon atoms (e.g., cyclopentanegroup or cyclohexane group, among others), the base name of thecycloalkane group having a defined number of cycloalkane ring carbonatoms refers to the unsubstituted cycloalkane group (including having nohydrocarbyl groups located on cycloalkane group ring carbon atom).Consequently, a substituted cycloalkane group having a specified numberof ring carbon atoms (e.g., substituted cyclopentane or substitutedcyclohexane, among others) refers to the respective group having one ormore substituent groups (including halogens, hydrocarbyl groups, orhydrocarboxy groups, among other substituent groups) attached to acycloalkane group ring carbon atom. When the substituted cycloalkanegroup having a defined number of cycloalkane ring carbon atoms is amember of the group of hydrocarbon groups (or a member of the generalgroup of cycloalkane groups), each substituent of the substitutedcycloalkane group having a defined number of cycloalkane ring carbonatoms is limited to hydrocarbyl substituent group. One can readilydiscern and select general groups, specific groups, and/or individualsubstituted cycloalkane group(s) having a specific number of ringcarbons atoms which can be utilized as member of the hydrocarbon group(or a member of the general group of cycloalkane groups).

The term “olefin” whenever used in this specification and claims refersto hydrocarbon compounds that have at least one carbon-carbon doublebond that is not part of an aromatic ring or an aromatic ring system.The term “olefin” includes aliphatic and aromatic, cyclic and acyclic,and/or linear and branched hydrocarbons having at least onecarbon-carbon double bond that is not part of an aromatic ring or ringsystem unless specifically stated otherwise. Olefins having only one,only two, only three, etc. carbon-carbon double bonds can be identifiedby use of the term “mono,” “di,” “tri,” etc. within the name of theolefin. The olefins can be further identified by the position of thecarbon-carbon double bond(s).

The term “alkene” whenever used in this specification and claims refersto a linear or branched aliphatic hydrocarbon olefin that has one ormore carbon-carbon double bonds. Alkenes having only one, only two, onlythree, etc. such multiple bonds can be identified by use of the term“mono,” “di,” “tri,” etc. within the name. Alkenes can be furtheridentified by the position of the carbon-carbon double bond(s). Otheridentifiers can be utilized to indicate the presence or absence ofparticular groups within an alkene. For example, a haloalkene refers toan alkene having one or more hydrogen atoms replaced with a halogenatom.

The term “alpha olefin” as used in this specification and claims refersto an olefin that has a carbon-carbon double bond between the first andsecond carbon atoms of the longest contiguous chain of carbon atoms. Theterm “alpha olefin” includes linear and branched alpha olefins unlessexpressly stated otherwise. In the case of branched alpha olefins, abranch can be at the 2-position (a vinylidene) and/or the 3-position orhigher with respect to the olefin double bond. The term “vinylidene”whenever used in this specification and claims refers to an alpha olefinhaving a branch at the 2-position with respect to the olefin doublebond. By itself, the term “alpha olefin” does not indicate the presenceor absence of other carbon-carbon double bonds unless explicitlyindicated. The term “linear alpha olefin” as used herein refers to anon-branched alpha olefin having a carbon-carbon double bond between thefirst and second carbon atom.

The term “normal alpha olefin” whenever used in this specification andclaims refers to a linear aliphatic mono-olefin having a carbon-carbondouble bond between the first and second carbon atoms. It is noted that“normal alpha olefin” is not synonymous with “linear alpha olefin” asthe term “linear alpha olefin” can include linear olefinic compoundshaving a double bond between the first and second carbon atoms andadditional double bonds.

An aliphatic compound is an acyclic or cyclic, saturated or unsaturated,carbon compound, excluding aromatic compounds. An “aliphatic group” is ageneralized group formed by removing one or more hydrogen atoms (asnecessary for the particular group) from the carbon atom of an aliphaticcompound. Aliphatic compounds and therefore aliphatic groups can containorganic functional group(s) and/or atom(s) other than carbon andhydrogen.

An aromatic compound is a compound containing a cyclically conjugateddouble bond system that follows the Hückel (4n+2) rule and contains(4n+2) pi-electrons, where n is an integer from 1 to 5. Aromaticcompounds include “arenes” (hydrocarbon aromatic compounds) and“heteroarenes,” also termed “hetarenes” (heteroaromatic compoundsformally derived from arenes by replacement of one or more methine (—C═)carbon atoms of the cyclically conjugated double bond system with atrivalent or divalent heteroatoms, in such a way as to maintain thecontinuous pi-electron system characteristic of an aromatic system and anumber of out-of-plane pi-electrons corresponding to the Hückel rule(4n+2). While arene compounds and heteroarene compounds are mutuallyexclusive members of the group of aromatic compounds, a compound thathas both an arene group and a heteroarene group are generally considereda heteroarene compound. Aromatic compounds, arenes, and heteroarenes canbe monocyclic (e.g., benzene, toluene, furan, pyridine, methylpyridine)or polycyclic unless otherwise specified. Polycyclic aromatic compounds,arenes, and heteroarenes, include, unless otherwise specified, compoundswherein the aromatic rings can be fused (e.g., naphthalene, benzofuran,and indole), compounds where the aromatic groups can be separate andjoined by a bond (e.g., biphenyl or 4-phenylpyridine), or compoundswhere the aromatic groups are joined by a group containing linking atoms(e.g., carbon of the methylene group in diphenylmethane; oxygen ofdiphenyl ether; nitrogen of triphenyl amine; among others linkinggroups). As disclosed herein, the term “substituted” can be used todescribe an aromatic group, arene, or heteroarene wherein a non-hydrogenmoiety formally replaces a hydrogen in the compound, and is intended tobe non-limiting.

An “aromatic group” refers to a generalized group formed by removing oneor more hydrogen atoms (as necessary for the particular group and atleast one of which is an aromatic ring carbon atom) from an aromaticcompound. For a univalent “aromatic group,” the removed hydrogen atommust be from an aromatic ring carbon. For an “aromatic group” formed byremoving more than one hydrogen atom from an aromatic compound, at leastone hydrogen atom must be from an aromatic hydrocarbon ring carbon.Additionally, an “aromatic group” can have hydrogen atoms removed fromthe same ring of an aromatic ring or ring system (e.g., phen-1,4-ylene,pyridin-2,3-ylene, naphth-1,2-ylene, and benzofuran-2,3-ylene), hydrogenatoms removed from two different rings of a ring system (e.g.,naphth-1,8-ylene and benzofuran-2,7-ylene), or hydrogen atoms removedfrom two isolated aromatic rings or ring systems (e.g.,bis(phen-4-ylene)methane).

An arene is aromatic hydrocarbon, with or without side chains (e.g.,benzene, toluene, or xylene, among others). An “aryl group” is a groupderived from the formal removal of a hydrogen atom from an aromatic ringcarbon of an arene. It should be noted that the arene can contain asingle aromatic hydrocarbon ring (e.g., benzene, or toluene), containfused aromatic rings (e.g., naphthalene or anthracene), and contain oneor more isolated aromatic rings covalently linked via a bond (e.g.,biphenyl) or non-aromatic hydrocarbon group(s) (e.g., diphenylmethane).Similarly, an “arylene group” refers to a group formed by removing twohydrogen atoms (at least one of which is from an aromatic ring carbon)from an arene. An “arene group” refers to a generalized group formed byremoving one or more hydrogen atoms (as necessary for the particulargroup and at least one of which is an aromatic ring carbon) from anarene. It should be noted that according the definitions providedherein, general arene groups (including an aryl group and an arylenegroup) include those having zero, one, or more than one hydrocarbylsubstituent groups located on an aromatic hydrocarbon ring or ringsystem carbon atom (e.g., a toluene group or a xylene group, amongothers) and is a member of the group of hydrocarbon groups. However, aphenyl group (or phenylene group) and/or a naphthyl group (ornaphthylene group) refer to the specific unsubstituted arene groups(including no hydrocarbyl group located on an aromatic hydrocarbon ringor ring system carbon atom). Consequently, a substituted phenyl group orsubstituted naphthyl group refers to the respective arene group havingone or more substituent groups (including halogens, hydrocarbyl groups,or hydrocarboxy groups, among others) located on an aromatic hydrocarbonring or ring system carbon atom. When the substituted phenyl groupand/or substituted naphtyl group is a member of the group of hydrocarbongroups (or a member of the general group of arene groups), eachsubstituent is limited to a hydrocarbyl substituent group. One havingordinary skill in the art can readily discern and select general phenyland/or naphthyl groups, specific phenyl and/or naphthyl groups, and/orindividual substituted phenyl or substituted naphthyl groups which canbe utilized as a member of the group of hydrocarbon groups (or a memberof the general group of arene groups).

An “aralkyl group” is an aryl-substituted alkyl group having a freevalance at a non-aromatic carbon atom (e.g., a benzyl group, or a2-phenyleth-1-yl group, among others). Similarly, an “aralkylene group”is an aryl-substituted alkylene group having two free valencies at asingle non-aromatic carbon atom or a free valence at two non-aromaticcarbon atoms while an “aralkane group” is a generalized aryl-substitutedalkane group having one or more free valencies at a non-aromatic carbonatom(s). It should be noted that according the definitions providedherein, general aralkane groups include those having zero, one, or morethan one hydrocarbyl substituent groups located on an aralkane aromatichydrocarbon ring or ring system carbon atom and is a member of the groupof hydrocarbon groups. However, specific aralkane groups specifying aparticular aryl group (e.g., the phenyl group in a benzyl group or a2-phenylethyl group, among others) refer to the specific unsubstitutedaralkane groups (including no hydrocarbyl group located on the aralkanearomatic hydrocarbon ring or ring system carbon atom). Consequently, asubstituted aralkane group specifying a particular aryl group refers toa respective aralkane group having one or more substituent groups(including halogens, hydrocarbyl groups, or hydrocarboxy groups, amongothers). When the substituted aralkane group specifying a particulararyl group is a member of the group of hydrocarbon groups (or a memberof the general group of aralkane groups), each substituent is limited toa hydrocarbyl substituent group. One can readily discern and selectsubstituted aralkane groups specifying a particular aryl group which canbe utilized as a member of the group of hydrocarbon groups (or a memberof the general group of aralkane groups).

A “primary carbon atom group,” a “secondary carbon atom group,” a“tertiary carbon atom group,” and a “quaternary carbon atom group”describe the type of carbon atom which would be created when the groupis attached to a base structure. A “primary carbon atom group” is agroup wherein the carbon atom bonded to the base structure is alsobonded to three monovalent atoms (e.g., hydrogen or halides) in additionto the base structure. A methyl group, a trifluormethyl group (amongother group) attached to a base structure represent potential “primarycarbon atom groups.” A “secondary carbon atom group” is a group whereinthe carbon atom bonded to the base structure is bonded to one othernon-monovalent atom (e.g., carbon, nitrogen, or oxygen, among others)and two monovalent atoms. An ethyl group, a 1-chloroeth-1-yl group, anda methoxymethyl group (among others) attached to a base structurerepresent potential “secondary carbon atom groups.” A “tertiary carbongroup” is a group wherein the carbon atom bonded to the base structureis bonded to two other non-monovalent atoms and one monovalent atom. Anisopropyl group, a 2-chloroprop-1-yl group, a phenyl group, and a1-methoxyethyl-1-yl group (among others) attached to a base structurerepresent potential “tertiary carbon groups.” A “quaternary carbongroup” is a group wherein the carbon atom bonded to the base structureis also bonded to three other non-monovalent atoms. A tert-butyl groupand a 2-methoxyprop-2-yl group (among others) attached to a basestructure represent potential “quaternary carbon groups.”

A “halide” has its usual meaning; therefore, examples of halides includefluoride, chloride, bromide, and iodide.

The terms “room temperature” or “ambient temperature” are used herein todescribe any temperature from 15° C. to 35° C. wherein no external heator cooling source is directly applied. Accordingly, the terms “roomtemperature” and “ambient temperature” encompass the individualtemperatures and any and all ranges, subranges, and combinations ofsubranges of temperatures from 15° C. to 35° C. wherein no externalheating or cooling source is directly applied. The term “atmosphericpressure” is used herein to describe an earth air pressure wherein noexternal pressure modifying means is utilized. Generally, unlesspracticed at extreme earth altitudes, “atmospheric pressure” is about 1atmosphere (alternatively, about 14.7 psi or about 101 kPa). Referencesto gaseous, liquid, and/or solid materials refer to the physical stateof the material at 25° C. and atmospheric pressure.

Features within this disclosure that are provided as minimum values canbe alternatively stated as “at least” or “greater than or equal to” anyrecited minimum value for the feature disclosed herein. Features withinthis disclosure that are provided as maximum values can be alternativelystated as “less than or equal to” for the feature disclosed herein.

Within this disclosure the normal rules of organic nomenclature willprevail. For instance, when referencing substituted compounds or groups,references to substitution patterns are taken to indicate that theindicated group(s) is (are) located at the indicated position and thatall other non-indicated positions are hydrogen. For example, referenceto a 4-substituted phenyl group indicates that there is a non-hydrogensubstituent located at the 4-position and hydrogens located at the 2, 3,5, and 6 positions. By way of another example, reference to a3-substituted naphth-2-yl indicates that there is a non-hydrogensubstituent located at the 3-position and hydrogens located at the 1, 4,5, 6, 7, and 8 positions. References to compounds or groups havingsubstitutions at positions in addition to the indicated position will bereferenced using comprising or some other alternative language. Forexample, a reference to a phenyl group comprising a substituent at the4-position refers to a group having a non-hydrogen atom at the4-position and hydrogen or any other non-hydrogen group at the 2-, 3-,5-, and 6-positions.

The term “reaction zone effluent,” and it derivatives (e.g.,oligomerization reaction zone effluent) generally refers to all thematerial which exits the reaction zone. The term “reaction zoneeffluent,” and its derivatives, can also be prefaced with otherdescriptors that limit the portion of the reaction zone effluent beingreferenced. For example, the term “reaction zone effluent” refers to allmaterial exiting the reaction zone (e.g., product and solvent ordiluent, among others), while the term “olefin reaction zone effluent”refers to only the olefins within the reaction zone effluent and theterm “oligomer product reaction zone effluent” refers to oligomerproduct within the reaction zone effluent.

The term “oligomerization,” and its derivatives, refers to processeswhich produce a mixture of products containing at least 70 weightpercent products containing from 2 to 30 ethylene units. Similarly, asused herein an “oligomer” is a product that contains from 2 to 30ethylene units while an “oligomerization product” or “oligomer product”includes all products made by the process including the “oligomers” andproducts which are not “oligomers” (e.g., products which contain morethan 30 ethylene units). Further the terms “oligomer product” and“oligomerization product” can be used interchangeably.

K value (sometimes referred to as Schulz-Flory chain growth factor, K,or Schulz-Flory K value) can be defined the equation: K=X_(q+1)/X_(q)wherein X_(q+1) is the number of moles of oligomer product producedhaving q+1 monomer (e.g., ethylene) units and X_(q) is the number ofmoles of oligomer product produced having q monomer (e.g., ethylene)units. Generally, the Schulz-Flory K value can be determined using anytwo oligomers of the oligomer product which differs in the number ofmonomer units by 1. However, one would appreciate that product isolationand analysis can lead to inaccuracies in a determined oligomer productdistribution using particular oligomers (e.g., incomplete recovery ofgaseous product and/or solid product during product isolation). Onehaving ordinary skill in the art would recognize such issues and canchoose the appropriate oligomers upon which to base the determination ofthe Schulz-Flory K value.

Catalyst system productivity is defined as grams of a product producedper gram (or mole) of heteroatomic ligand metal salt complex orheteroatomic ligand in the catalyst system utilized in theoligomerization. Catalyst system activity is defined as grams of aproduct produced per gram (or mole) of heteroatomic ligand metal saltcomplex or heteroatomic ligand utilized per unit of time (e.g., hour) ofan oligomerization. Catalyst system productivity and/or activity can bestated in terms of various products of an oligomerization and/orcomponents of catalyst system. For example, in an ethyleneoligomerization process utilizing a catalyst system comprising an ironsalt complex and an organoaluminum compound, the catalyst systemproductivity which can be utilized include (g oligomer product)/(g Fe),among other productivities.

Unless otherwise specified, the terms “contacted,” “combined,” and “inthe presence of” refer to any addition sequence, order, or concentrationfor contacting or combining the recited two or more components. Thecombining or contacting of the components, according to the variousmethods described herein can occur in one or more contact zones undersuitable contact conditions such as temperature, pressure, contact time,flow rates, etc. . . . . The contact zone can be disposed in a vessel(e.g., a storage tank, tote, container, mixing vessel, reactor, etc.), alength of pipe (e.g., a tee, inlet, injection port, or header forcombining component feed lines into a common line), or any othersuitable apparatus for bringing the components into contact, unlessotherwise specified. The processes can be carried out in a batch orcontinuous process as is suitable for a given aspect, unless otherwisespecified.

Use of the term “optionally” with respect to any element of a claim isintended to mean that the subject element is required, or alternatively,is not required. Both alternatives are intended to be within the scopeof the claim.

In this disclosure, a process can have multiple steps or can includefeatures having a number of different elements (e.g., components in acatalyst system or components in an olefin oligomerization process,among other features). These steps and/or elements can be designatedutilizing the series a), b), c), etc., i), ii), iii), etc., (a), (b),(c), etc., and/or (i), (ii), (iii), etc. (among other designationseries) as necessary to provide a designation for each process stepand/or element. It should be understood that the numerical oralphabetical precedence of the designations within a designation seriesdoes not imply a particular order or preference of the process step in aprocess described herein, the feature(s) described herein, and/or anelement(s) in a feature unless specifically specified otherwise ornecessitated by other process steps, elements, and/or element features.Additionally, these designations series are provided to differentiatedifferent process steps and/or elements in a feature and can be utilizedas necessary, and without regard to the designation series utilized fora particular step, element, or feature utilized within this descriptionas long as the designation series consistently distinguish differentfeatures, different process steps, and/or different elements of afeature.

The terms “simultaneously,” “simultaneously contact,” “contactsimultaneously,” and their derivatives when referring to a contactmethod refers to a contact method wherein the two or more recitedcompounds, mixtures, streams, and/or compositions are contacted byflowing into a common junction, pot, vessel, or reactor, among others,at the same time. The terms “substantially simultaneously,”“substantially simultaneously contact,” “contact substantiallysimultaneously,” and their derivatives when referring to a contactmethod refers to a contact method wherein, during the contact of two ormore recited compounds, mixtures, streams, and/or compositions, the twoor more recited compounds, mixtures, streams, and/or compositions arecontacted such that for some period during the contact process the twoor more recited compounds, mixtures, streams, and/or compositions flowinto a common junction, pot, vessel, or reactor at the same time. Itshould be noted that the terms “substantially simultaneously,”“substantially simultaneously contact,” “contact substantiallysimultaneously,” and their derivatives do not mean that the two or morerecited compounds, mixtures, streams, and/or compositions are contactedsimultaneously over the entire addition of each of the two or morerecited compounds, mixtures, streams, and/or compositions. The terms“substantially simultaneously,” “substantially simultaneously contact,”“contact substantially simultaneously,” and it derivatives includescenarios where the flow of one of the (or less than all of the) recitedcompounds, mixtures, streams, and/or compositions can be initiated intothe common junction, pot, vessel, or reactor before the others and/orthe flow of one of the (or less than all of the) recited compounds,mixtures, streams, and/or compositions into the common junction, pot,vessel, or reactor can be completed, stopped, or discontinued before theother recited compounds, mixtures, streams, and/or compositions. In anyaspect and/or embodiment described herein, the terms “simultaneously,”“simultaneously contact,” “contact simultaneously,” and theirderivatives, can be modified by the inclusion of a term providing aquantity of the each of the recited compounds, mixtures, streams, and/orcompositions which can be contacted simultaneously indicate scenarios ofvarious degrees of “substantially simultaneously,” “substantiallysimultaneously contact,” “contact substantially simultaneously,” andtheir derivatives. For example, at least 20%, 30%, 40%, 50%, 60%, 70%,75%, 80%, 85%, 90%, 95% of each of the recited compounds, mixtures,streams, and/or compositions can be “simultaneously contacted” or“contacted simultaneously.” Generally, the percentages of the recitedcompounds, mixtures, streams, and/or compositions that can be“simultaneously contacted” or “contacted simultaneously” can be byweight (wt. %), by volume (volume %), or by mole (mole %). Unlessotherwise specified, recited compounds, mixtures, streams, and/orcompositions that are “substantially simultaneously,” “substantiallysimultaneously contact,” “contact substantially simultaneously,” andtheir derivatives shall mean that at least 50% of each of the recitedcompounds, mixtures, streams, and/or compositions can be “simultaneouslycontacted” or “contacted simultaneously.”

It should be further noted, that in reference to contact method orprocess, “simultaneously,” “simultaneously contact,” “contactsimultaneously,” “substantially simultaneously contact,” “contactsubstantially simultaneously,” and their derivatives is different than aprocess or method wherein one or more a first materials (e.g., compound,mixture, stream, and/or composition) already resides in a pot, vessel,or reactor and one or more other compounds, mixtures, streams, and/orcompositions are added to the pot, vessel, or reactor. In this instancethe first material in the pot, vessel, or reactor does not flow into thepot, vessel, or reactor concurrently with the other compounds, mixtures,streams, and/or compositions and the material in the pot. Thus, thefirst material and the other compounds, mixtures, streams, and/orcompositions cannot be said to be “simultaneously contacted,” “contactedsimultaneously,” “substantially simultaneously contacted,” or “contactedsubstantially simultaneously.” with the other component(s).

Disclosed herein are processes comprising a) introducing into a reactionzone (i) ethylene, (ii) a heteroatomic ligand first metal salt complex,(iii) a second metal salt, and (iv) an organoaluminum compound; and b)forming an oligomer product. In an aspect, the heteroatomic ligand firstmetal salt complex comprises a heteroatomic ligand complexed to a firstmetal salt. Also disclosed herein, are processes comprising a)introducing into a reaction zone (i) ethylene, (ii) a heteroatomicligand, (iii) a metal salt, and (iv) an organoaluminum compound; and b)forming an oligomer product. In some embodiments, these processes can beprocesses for forming an oligomer product. Further disclosed herein isthe use of a metal salt (or second metal salt depending on theparticular process) for improving the productivity of any process (e.g.,processes for forming an oligomer product) disclosed herein. Theprocesses further can comprise an optional introduction of hydrogen intothe reaction zone. The processes further can comprise an optionalintroduction of an organic reaction medium. In a still further aspect,the organo groups of the organoaluminum compound can be substantiallydevoid of β,γ-branched organo groups and/or β,δ-branched organo groups.Optionally, the ethylene, the heteroatomic ligand first metal saltcomplex, the heteroatomic ligand, the first metal salt, the metal salt,and hydrogen can be contacted with or in one or more organic reactionmedium(s). In an aspect, the oligomer product can be formed at, thereaction zone can have, or the reaction zone can operate at, conditionscapable of forming an oligomer product. Generally, the heteroatomicligand first metal salt complex, the heteroatomic ligand of theheteroatomic ligand first metal salt complex, the first metal salt ofthe heteroatomic ligand first metal salt complex, the second metal salt,the heteroatomic ligand, the metal salt, the organoaluminum compound,the optional hydrogen, the optional organic reaction medium(s), thereaction zone, the oligomer product, the conditions at which theoligomer product can be formed, the conditions at which the reactionzone can have, and/or the conditions at which the reaction can operate,where applicable, are independent elements of the processes describedherein and are independently described herein. These independentlydescribed process elements can be utilized in any combination, andwithout limitation, to further describe the processes provided herein.

Generally, the heteroatomic ligand and metal salt or the heteroatomicligand first metal salt complex can be any heteroatomic ligand and metalsalt or any heteroatomic ligand first metal salt complex that whencontacted with ethylene as disclosed herein can form an oligomerproduct. In an aspect, the processes described herein utilize aheteroatomic ligand first metal salt complex; or alternatively, aheteroatomic ligand and a metal salt. In an aspect, the heteroatomicligand or the heteroatomic ligand of the heteroatomic ligand first metalsalt complex can comprise a bidentate metal salt complexing moiety or atridentate metal salt complexing moiety; alternatively, a bidentatemetal salt complexing moiety; or alternatively, a tridentate metal saltcomplexing moiety. In an embodiment, the heteroatomic ligand or theheteroatomic ligand of the heteroatomic ligand first metal salt complexcan comprise at least one metal salt complexing moiety; alternatively,one or two metal salt complexing moieties; alternatively, one metal saltcomplexing moiety; or alternatively, two metal salt complexing moieties.

In an aspect, each metal salt complexing moiety of the heteroatomicligand or the heteroatomic ligand of the heteroatomic ligand first metalsalt complex, can comprise at least two metal salt complexing groupsselected from the group consisting of an imine group and an aromaticnitrogen atom containing group. In some embodiments, each metal saltcomplexing moiety of the heteroatomic ligand or the heteroatomic ligandof the heteroatomic ligand first metal salt complex, can comprise atleast two imine metal salt complexing group, at least two iminecomplexing groups and an aromatic nitrogen atom containing group, or animine group and an aromatic nitrogen atom containing group;alternatively, at least two imine metal salt complexing group;alternatively, at least two imine complexing groups and an aromaticnitrogen atom containing group; or alternatively, an imine group and anaromatic nitrogen atom containing group. Generally, the aromaticnitrogen atom containing group of any metal salt complexing moiety ofthe heteroatomic ligand or the heteroatomic ligand of the heteroatomicligand first metal salt complex can be a pyrrole group, a pyridinegroup, a bipyridine (2,2′-bipyridine) group, or a phenanthroline group;alternatively, a pyridine group, a bipyridine (2,2′-bipyridine) group,or a phenanthroline group; alternatively, a pyridine group or aphenanthroline group; alternatively, a pyridine group; alternatively, abipyridine (2,2′-bipyridine) group; or alternatively, a phenanthrolinegroup. In an embodiment, the pyrrole group, pyridine group, bipyridine(2,2′-bipyridine) group, or phenanthroline group can be unsubstituted orsubstituted; alternatively, unsubstituted; or alternatively,substituted. Each substituent of a substituted pyrrole group, asubstituted pyridine group, a substituted bipyridine (2,2′-bipyridine)group, or a substituted phenanthroline group independently can be ahalide, an alkyl group, or a hydrocarboxy group; alternatively, a halideor an alkyl group; alternatively, a halide or a hydrocarboxy group;alternatively, an alkyl group or a hydrocarboxy group; alternatively, ahalide; alternatively, an alkyl group; or alternatively, a hydrocarboxygroup. Halides, alkyl groups (general and specific), and hydrocarboxygroups (general and specific) that can be utilized as substituents areindependently disclosed herein and can be utilized without limitation,and in any combination, to further describe a substituted pyrrole group,a substituted pyridine group, a substituted bipyridine (2,2′-bipyridine)group, or a substituted phenanthroline group.

In an aspect, the heteroatomic ligand or the heteroatomic ligand of theheteroatomic ligand first metal salt complex can be an α-diimine, apyridine bisimine, a phenanthroline imine, or any combination thereof;alternatively, an α-diimine or a pyridine bisimine; alternatively, anα-diimine; alternatively, a pyridine bisimine; or alternatively, aphenanthroline imine. In some embodiments, the heteroatomic ligand firstmetal salt complex can be an α-diimine first metal salt complex, apyridine bisimine first metal salt complex, a phenanthroline imine firstmetal salt complex, or any combination thereof; alternatively, anα-diimine first metal salt complex; alternatively, a pyridine bisiminefirst metal salt complex; or alternatively, a phenanthroline imine firstmetal salt complex. Generally, the α-diimine, the pyridine bisimine, thephenanthroline imine, the α-diimine first metal salt complex, thepyridine bisimine first metal salt complex, and the phenanthroline iminefirst metal salt complex are independent elements of any respectiveprocesses described herein in which they are utilized and areindependently described herein. These independently described elementscan be utilized in any combination, and without limitation, to furtherdescribe the processes which utilize these independent elements.

In various aspects and embodiments, an α-diimine and a metal salt, or anα-diimine first metal salt complex, can be utilized in the processesdescribed herein. Generally, the α-diimine, or the α-diimine of theα-diimine first metal salt complex disclosed herein, can be anyα-diimine, or any α-diimine of the α-diimine first metal salt complexdisclosed herein, that when contacted with the other materials of theprocesses described herein (e.g., metal salt, ethylene, organoaluminumcompound and/or any other appropriate reagent(s)), under the appropriateconditions, can form an oligomer product. Generally, the α-diimine andthe metal salt (or the α-diimine and the first metal salt of theα-diimine first metal salt complex) are independent elements of theprocesses described herein and are independently disclosed herein. Theindependent descriptions of the α-diimine and the metal salt (or theα-diimine and the first metal salt of the α-diimine first metal saltcomplex) can be used without limitation, and in any combination, tofurther describe the processes that can be utilized in the aspectsand/or embodiments of the processes described herein. In an aspect, theα-diimine (or the α-diimine of the α-diimine first metal salt complex)can comprise only one α-diimine group; alternatively, at least twoα-diimine groups; or alternatively, the α-diimine can comprise only twoα-diimine groups.

Generally, the α-diimine or the α-diimine of the α-diimine first metalsalt complex can be described as comprising i) an α-diimine group, ii) afirst imine nitrogen group attached to a first imine nitrogen atom ofthe α-diimine group, and iii) a second imine nitrogen group attached toa second imine nitrogen atom of the α-diimine group. The α-diiminegroup, first imine nitrogen group, and second imine nitrogen group areindependent elements of the α-diimine or the α-diimine of the α-diiminefirst metal salt complex and each of these elements are independentlydescribed herein. The independent elements of the α-diimine or theα-diimine of the α-diimine first metal salt complex can used withoutlimitation, and in any combination, to further describe the α-diimine orthe α-diimine of the α-diimine first metal salt complex.

In an aspect, the α-diimine (or the α-diimine of the α-diimine firstmetal salt complex) can be a bidentate α-diimine or a tridentateα-diimine; alternatively, a bidentate α-diimine; or alternatively, atridentate α-diimine. It should be noted that the tridentate α-diiminedescription does not necessarily imply that all of the ligating elementsof the tridentate α-diimine complex to the metal salt.

In an aspect, the α-diimine group of the α-diimine (or the α-diimine ofthe α-diimine first metal salt complex) can be derived from an α-diacylcompound; or alternatively, an α-dione. Consequently, in some aspects,the α-diimine (or the α-diimine of the α-diimine first metal saltcomplex) can be described as comprising i) an α-diimine group derivedfrom an α-diacyl compound, ii) a first imine nitrogen group attached toa first imine nitrogen atom of the α-diimine group, and iii) a secondimine nitrogen group attached to a second imine nitrogen atom of theα-diimine group; or alternatively, the α-diimine (or the α-diimine ofthe α-diimine first metal salt complex) can be described as comprisingi) an α-diimine group derived from an α-dione, ii) a first iminenitrogen group attached to a first imine nitrogen atom of the α-diiminegroup, and iii) a second imine nitrogen group attached to a second iminenitrogen atom of the α-diimine group. In an aspect, the α-diacylcompound (or α-dione) can be an aliphatic α-diacyl compound (oraliphatic α-dione) or an aromatic α-diacyl compound (or aromaticα-dione); alternatively, an aliphatic α-diacyl compound (or aliphaticα-dione); or alternatively, an aromatic α-diacyl compound (or aromaticα-dione). In other aspects, the α-diacyl compound (or α-dione), whetherit is aliphatic or aromatic, can be a cyclic α-diacyl compound (orcyclic α-dione) or an acyclic α-diacyl compound (or acyclic α-dione);alternatively, a cyclic α-diacyl compound (or cyclic α-dione); oralternatively, an acyclic α-diacyl compound (or acyclic α-dione). In anyaspect or embodiment disclosed herein, the α-diacyl compound (orα-dione), whether it is aliphatic or aromatic and/or cyclic or acyclic,can be a C₄ to C₆₀ α-diacyl compound (or C₄ to C₆₀ α-dione), a C₄ to C₄₅α-diacyl compound (or C₄ to C₄₅ α-dione), a C₄ to C₃₀ α-diacyl compound(or C₄ to C₃₀ α-dione), or C₄ to C₂₀ α-diacyl compound (or C₄ to C₂₀α-dione).

Generally, the α-dione can have the structure R^(k1)—C(═O)—C(═O)—R^(k2).In an aspect, R^(k1) and R^(k2) independently can be an organyl group;alternatively, an organyl group consisting essentially of inertfunctional groups; or alternatively, a hydrocarbyl group. In any aspector embodiment disclosed herein, the organyl groups which can be utilizedas R^(k1) and/or R^(k2) can be a C₁ to C₃₀, a C₁ to C₂₀, a C₁ to C₁₅, aC₁ to C₁₀, or a C₁ to C₅ organyl group. In any aspect or embodimentdisclosed herein, the organyl groups consisting essentially of inertfunctional groups which can be utilized as R^(k1) and/or R^(k2)independently can be a C₁ to C₃₀, a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀,or a C₁ to C₅ organyl group consisting essentially of inert functionalgroups. In any aspect or embodiment disclosed herein, the hydrocarbylgroups which can be utilized as R^(k1) and/or R^(k2) independently canbe a C₁ to C₃₀, a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅hydrocarbyl group.

In an aspect, the α-dione from which the α-diimine group (or theα-diimine of the α-diimine first metal salt complex) can be derived canbe an acyclic α-dione, a semicyclic α-dione, or a cyclic α-dione;alternatively, an acyclic α-dione; alternatively, a semicyclic α-dione;or alternatively, a cyclic α-dione. When the α-dione is an acyclicα-dione, both R^(k1) and R^(k2) are acyclic. When the α-dione is asemi-cyclic α-dione, R^(k1) and/or R^(k2) are or can comprise a cyclicstructure wherein R^(k1) and R^(k2) are not connected to form a ring orring system containing both ketone carbon atoms of the α-dione group.When the α-dione is a cyclic α-dione, R^(k1) and R^(k2) are connected toform a ring or ring system containing both ketone carbon atoms of theα-dione group. In some semi-cyclic and/or cyclic α-dione aspects, thering or ring system(s) can be saturated. In other semi-cyclic and/orcyclic α-dione aspects, the ring or ring system(s) can containcarbon-carbon double (and/or triple) bonds. In further semi-cyclicand/or cyclic α-dione aspects, the ring or ring system(s) can be abicyclic ring system. In yet other semi-cyclic and/or cyclic α-dioneaspects, the ring or ring system(s) can comprise an aromatic ring or anaromatic ring system.

In an acyclic α-dione aspect, the α-dione can be 2,3-butanedione, asubstituted 2,3-butanedione, 2,3-pentanedione, a substituted2,3-pentanedione, 2,3-hexanedione, a substituted 2,3-hexanedione,3,4-hexanedione, or a substituted 3,4-hexanedione. In some aspects, theα-dione can be 2,3-butanedione, 2,3-pentanedione, 2,3-hexanedione, or3,4-hexanedione. In further aspects, the α-dione can be 2,3-butanedione;alternatively, 2,3-pentanedione; alternatively, 2,3-hexanedione; oralternatively, 3,4-hexanedione.

In an aromatic semi-cyclic α-dione aspect, the α-dione can be benzil ora substituted benzil. In other aspects, the α-dione can be benzil.

In a saturated cyclic α-dione aspect, the α-dione can be1,2-cyclobutanedione, a substituted 1,2-cyclobutanedione,1,2-cyclopentanedione, a substituted 1,2-cyclopentanedione,1,2-cyclohexanedione, a substituted 1,2-cyclohexanedione,1,2-cycloheptanedione, or a substituted 1,2-cycloheptanedione. In somesaturated cyclic α-dione aspects, the α-dione can be1,2-cyclopentanedione, a substituted 1,2-cyclopentanedione,1,2-cyclohexanedione, or a substituted 1,2-cyclohexanedione. In somesaturated cyclic α-dione aspects, the α-dione can be1,2-cyclopentanedione, or 1,2-cyclohexanedione. In yet other aspects,the α-dione can be 1,2-cyclopentanedione; or alternatively,1,2-cyclohexanedione.

In saturated ring system α-dione aspects, the α-dione can bebicyclo[2.2.1]hepta-1,2-dione, a substitutedbicyclo[2.2.1]hepta-1,2-dione, bicyclo[2.2.2]octa-1,2-dione, asubstituted bicyclo[2.2.2]octa-1,2-dione, or camphorquinone. In somesaturated ring system aspects, the α-dione can bebicyclo[2.2.1]hepta-1,2-dione, bicyclo[2.2.2]octa-1,2-dione, orcamphorquinone. In yet other saturated ring system α-dione aspects, theα-dione can be camphorquinone.

In unsaturated cyclic α-dione aspects, the α-dione can be1,2-benzoquinone, a substituted 1,2-benzoquinone,cyclohex-3-ene-1,2-dione, a substituted cyclohex-3-ene-1,2-dione,cyclopent-3-ene-1,2-dione, a substituted cyclopent-3-ene-1,2-dione,cyclohex-4-ene-1,2-dione, a substituted cyclohex-4-ene-1,2-dione,3,4-dihydro-1,2-naphthoquinone, a substituted3,4-dihydro-1,2-naphtha-quinone, 1,4-dihydronaphthoquinone, or asubstituted 1,4-dihydronaphthoquinone. In some unsaturated cyclicα-dione aspects, the α-dione can be 1,2-benzoquinone,cyclohex-3-ene-1,2-dione, cyclopent-3-ene-1,2-dione,cyclohex-4-ene-1,2-dione, 3,4-dihydronaphthoquinone, or1,4-dihydronaphthoquinone. In other unsaturated cyclic α-dione aspects,the α-dione can be 1,2-benzoquinone; alternatively,3,4-dihydronaphthoquinone; or alternatively,1,4-dihydronaphthanoquinone.

In aromatic ring system α-dione aspects, the α-dione can be a1,2-naphthoquinone, a substituted 1,2-naphthoquinone,2,3-naphthoquinone, a substituted 2,3-naphthoquinone,acenaphthenequinone, a substituted acenaphthenequinone,phenanthrenequinone, a substituted phenanthrenequinone, pyrenequinone,or a substituted pyrenequinone. In some aromatic ring system α-dioneaspects, the α-dione can be 1,2-naphthoquinone, 2,3-naphthoquinone,acenaphthenequinone, phenanthrenequinone, or pyrenequinone. In otheraromatic ring system α-dione aspects, the α-dione can beacenaphthenequinone, phenanthrenequinone, or pyrenequinone. In yet otheraromatic ring system α-dione aspects, the α-dione can be1,2-naphthoquinone; alternatively, 2,3-naphthoquinone; alternatively,acenaphthenequinone; alternatively, phenanthrenequinone; oralternatively, pyrenequinone.

Within any substituted α-dione aspects, each substituent independentlycan be a halide, an alkyl group, or a hydrocarboxy group; alternatively,a halide or an alkyl group; alternatively, a halide or a hydrocarboxygroup; alternatively, an alkyl group or a hydrocarboxy group;alternatively, a halide; alternatively, an alkyl group; oralternatively, a hydrocarboxy group. Halides, alkyl groups (general andspecific), and hydrocarboxy groups (general and specific) that can beutilized as substituents are independently disclosed herein and can beutilized without limitation, and in any combination, to further describethe substituent of any substituted α-dione described herein.

In an aspect, the first imine group attached to the first imine nitrogenatom (first imine group for short) and/or second imine group attached tothe second imine nitrogen atom (second imine group for short) of theα-diimine independently can be an organyl group; alternatively, anorganyl group consisting essentially of inert functional groups; oralternatively, a hydrocarbyl group.

Generally, a bidentate α-diimine will have a first imine group and asecond imine group which can be independently selected from an organylgroup consisting essentially of inert functional groups (or ahydrocarbyl group). Thus, when the α-diimine is a bidentate α-diimine,the bidentate α-diimine can comprise i) an α-diimine group, ii) a firstimine nitrogen group consisting of an organyl group consistingessentially of inert functional groups (or a hydrocarbyl group) attachedto a first imine nitrogen atom of the α-diimine group and iii) a secondimine nitrogen group consisting of an organyl group consistingessentially of inert functional groups (or a hydrocarbyl group) attachedto a second imine nitrogen atom of the α-diimine group.

Generally, a tridentate α-diimine will have a first imine group selectedfrom an organyl group consisting essentially of inert functional groups(or a hydrocarbyl group) while the second imine group is an organylgroup. When the α-diimine is a tridentate α-diimine, the organyl groupwhich is the second imine group can be described as a second imine groupcomprising (1) a metal salt complexing group (or a first metal saltcomplexing group for the α-diimine first metal salt complex) and (2) alinking group linking the metal salt complexing group (or the firstmetal salt complexing group for the α-diimine first metal salt complex)to a second imine nitrogen atom of the α-diimine group. Thus, in someaspects, the tridentate α-diimine can comprise i) an α-diimine group,ii) a first imine nitrogen group consisting of an organyl groupconsisting essentially of inert functional groups (or a hydrocarbylgroup) attached to a first imine nitrogen atom of the α-diimine group,and iii) a second imine nitrogen group comprising (1) a metal saltcomplexing group (or the first metal salt complexing group for theα-diimine first metal salt complex) and (2) a linking group linking themetal salt complexing group (or the first metal salt complexing groupfor the α-diimine first metal salt complex) to a second imine nitrogenatom of the α-diimine group. The metal salt complexing group and thelinking group (or the first metal salt complexing group and the linkinggroup for the α-diimine first metal salt complex) of the second iminegroup comprising (1) a metal salt complexing group (or the first metalsalt complexing group for the α-diimine first metal salt complex) and(2) a linking group linking the metal salt complexing group or the firstmetal salt complexing group for the α-diimine first metal salt complex)to a second imine nitrogen atom of the α-diimine group are independentelements of the second imine group and are independently describedherein. The independent description of the metal salt complexing group(or the first metal salt complexing group for the α-diimine first metalsalt complex) and the linking group can be used without limitation andin any combination to further describe the second imine group comprising(1) a metal salt complexing group (or the first metal salt complexinggroup for the α-diimine first metal salt complex) and (2) a linkinggroup linking the metal salt complexing group or the first metal saltcomplexing group for the α-diimine first metal salt complex) to a secondimine nitrogen atom of the α-diimine group of an α-diimine.

In any aspect and/or embodiment disclosed herein, the organyl groupswhich can be utilized as the first and/or second imine organyl groupsindependently can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ toC₅ organyl group. In any aspect and/or embodiment disclosed herein, theorganyl groups consisting essentially of inert functional groups whichcan be utilized as the first and/or second imine organyl groupsconsisting essentially of inert functional groups independently can be aC₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl groupconsisting essentially of inert functional groups. In any aspect and/orembodiment disclosed herein, the hydrocarbyl groups which can beutilized as the first and/or second imine hydrocarbyl groupsindependently can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ toC₅ hydrocarbyl group. Generally, the first imine group and the secondimine group independently can be saturated or unsaturated, linear orbranched, acyclic or cyclic, and/or aromatic or heteroaromatic. In otheraspects, the first imine group and/or second imine group, can be aprimary, a secondary, a tertiary, or a quaternary group; alternatively,a primary group; alternatively, a secondary group; alternatively, atertiary group; or alternatively, a quaternary group. One skilled in theart will readily recognize which imine nitrogen groups belong to theprimary, secondary, tertiary, or quaternary imine nitrogen groupclasses.

In an aspect, the first imine group and/or second imine groupindependently can be an alkyl group, a substituted alkyl group, acycloalkyl group, a substituted cycloalkyl group, an aryl group, or asubstituted aryl group. In some aspects, the first imine group and/orsecond imine group independently can be an alkyl group or a substitutedalkyl group; alternatively, a cycloalkyl group or a substitutedcycloalkyl group; alternatively, an aryl group or a substituted arylgroup; or alternatively, an alkyl group, a cycloalkyl group, or an arylgroup. In other aspects, the first imine group and/or second imine groupindependently can be an alkyl group; alternatively, a substituted alkylgroup, alternatively, a cycloalkyl group; alternatively, a substitutedcycloalkyl group; alternatively, an aryl group; or alternatively, asubstituted aryl group. In any aspect and/or embodiment disclosedherein, the alkyl group which can be utilized as the first imine groupand/or second imine group can be a C₁ to C₂₀, a C₁ to C₁₀, or a C₁ to C₅alkyl group. In any aspect and/or embodiment disclosed herein, thesubstituted alkyl group which can be utilized as the first imine groupand/or second imine group can be a C₁ to C₂₀, a C₁ to C₁₀, or a C₁ to C₅substituted alkyl group. In any aspect and/or embodiment disclosedherein, the cycloalkyl group which can be utilized as the first iminegroup and/or second imine group can be a C₄ to C₂₀, a C₄ to C₁₅, or a C₄to C₁₀ cycloalkyl group. In any aspect and/or embodiment disclosedherein, the substituted cycloalkyl group which can be utilized as thefirst imine group and/or second imine group can be a C₄ to C₂₀, a C₄ toC₁₅, or a C₄ to C₁₀ substituted cycloalkyl group. In any aspect and/orembodiment disclosed herein, the aryl group which can be utilized as thefirst imine group and/or second imine group can be a C₆ to C₂₀, a C₆ toC₁₅, or a C₆ to C₁₀ aryl group. In any aspect and/or embodimentdisclosed herein, the substituted aryl group which can be utilized asthe first imine group and/or second imine group can be a C₆ to C₂₀, a C₆to C₁₅, or a C₆ to C₁₀ substituted aryl group. Each substituent of asubstituted alkyl group (general or specific), a substituted cycloalkylgroup (general or specific), a substituted aryl group (general orspecific), and/or substituted aryl group (general or specific) can be ahalogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, ahalogen or a hydrocarbyl group; alternatively, a halogen or ahydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxygroup; alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe the first imine group and/or second imine group.

In an aspect, the first imine nitrogen group and/or the second iminenitrogen group independently can be a methyl group, an ethyl group, apropyl group, a butyl group, or a pentyl group. In some aspects, thefirst imine nitrogen group and/or the second imine nitrogen groupindependently can be a methyl group, an ethyl group, an n-propyl group,an isopropyl group, an n-butyl group, a sec-butyl group, an isobutylgroup, a tert-butyl group, an n-pentyl group, a 2-pentyl group, a3-pentyl group, a 2-methyl-1-butyl group, a tert-pentyl group, a3-methyl-1-butyl group, a 3-methyl-2-butyl group, or a neo-pentyl group.In some aspects, the alkyl groups which can be utilized as the firstimine nitrogen group and/or the second imine nitrogen group can besubstituted. Each substituent of a substituted alkyl group (general orspecific) independently can be a halogen or a hydrocarboxy group;alternatively, a halogen; or alternatively, a hydrocarboxy group.Substituent halogens and substituent hydrocarboxy groups (general andspecific) are independently disclosed herein. These substituent halogensand substituent hydrocarboxy groups can be utilized without limitationto further describe a substituted alkyl group (general or specific)which can be utilized as the first imine nitrogen group and/or thesecond imine nitrogen group.

In an aspect, the first imine nitrogen group and/or the second iminenitrogen group can be a cyclopentyl group, a substituted cyclopentylgroup, a cyclohexyl group, a substituted cyclohexyl group, an adamantylgroup, or a substituted adamantyl group; alternatively, a cyclopentylgroup or a substituted cyclopentyl group; alternatively, a cyclohexylgroup or a substituted cyclohexyl group; alternatively, an adamantylgroup or a substituted adamantyl group; alternatively, a cyclopentylgroup; alternatively, a substituted cyclopentyl group; alternatively, acyclohexyl group; alternatively, a substituted cyclohexyl group;alternatively, an adamantyl group; or alternatively, a substitutedadamantyl group. Each substituent of a substituted cycloalkyl grouphaving a specified number of ring carbon atoms independently can be ahalogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, ahalogen or a hydrocarbyl group; alternatively, a halogen or ahydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxygroup; alternatively, a halogen, alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxy(general and specific) groups are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe a substituted cycloalkyl group (general or specific) which canbe utilized as the first imine nitrogen group and/or the second iminenitrogen group.

In an aspect, the first imine nitrogen group and/or the second iminenitrogen group can be a phenyl group, a substituted phenyl group, anaphthyl group, or a substituted naphthyl group; alternatively, a phenylgroup or a substituted phenyl group; alternatively, a naphthyl group, ora substituted naphthyl group; alternatively, a phenyl group;alternatively, a substituted phenyl group; alternatively, a naphthylgroup; or alternatively, a substituted naphthyl group. In an aspect,each substituted phenyl group which can be the first imine nitrogengroup and/or the second imine nitrogen group can comprise a substituentat the 2-position, a substituent at the 3-position, a substituent at the4-position, substituents at the 2- and 3-positions, substituents at the2- and 4-positions, substituents at the 2- and 5-positions, substituentsat the 3- and 5-positions, substituents at the 2- and 6-positions, orsubstituents at the 2-, 4-, and 6-positions; alternatively, asubstituent at the 2-position, a substituent at the 4-position,substituents at the 2- and 4-positions, substituents at the 2- and6-positions, or substituents at the 2-, 4-, and 6-positions;alternatively, substituents at the 2- and 6-positions or substituents atthe 2-, 4-, and 6-positions; alternatively, a substituent at the2-position; alternatively, a substituent at the 3-position;alternatively, a substituent at the 4-position; alternatively,substituents at the 2- and 3-positions; alternatively, substituents atthe 2- and 4-positions; alternatively, substituents at the 2- and5-positions; alternatively, substituents at the 3- and 5-positions;alternatively, substituents at the 2- and 6-positions; or alternatively,substituents at the 2-, 4-, and 6-positions. In some aspects, thesubstituted phenyl group, which can be utilized as the first iminenitrogen group and/or the second imine nitrogen group, can be a2-substituted phenyl group, a 3-substituted phenyl group, a4-substituted phenyl group, a 2,3-disubstituted phenyl group, a2,4-disubstituted phenyl group, a 2,5-disubstituted phenyl group, a3,5-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2-substituted phenylgroup, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group;alternatively, a 2,6-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2-substituted phenylgroup; alternatively, a 4-substituted phenyl group; alternatively, a2,3-disubstituted phenyl group; alternatively, a 2,4-disubstitutedphenyl group; alternatively, a 2,5-disubstituted phenyl group;alternatively, a 3,5-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; or alternatively, a 2,4,6-trisubstitutedphenyl group. In an aspect, one or more substituents of amulti-substituted phenyl group utilized as the first imine nitrogengroup and/or the second imine nitrogen group can be the same ordifferent; alternatively, all the substituents of a multi-substitutedphenyl group can be the same; or alternatively, all the substituents ofa multi-substituted phenyl group can be different. Each substituent of asubstituted phenyl group (general or specific) independently can be ahalogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, ahalogen or a hydrocarbyl group; alternatively, a halogen or ahydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxygroup; alternatively, a halogen, alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe a substituted phenyl group (general or specific) which can beutilized as the first imine nitrogen group and/or the second iminenitrogen group.

In a non-limiting aspect, the substituted phenyl group, which can beutilized as the first imine nitrogen group and/or the second iminenitrogen group can be a 2-alkylphenyl group, a 3-alkylphenyl group, a4-alkylphenyl group, a 2,3-dialkylphenyl group, a 2,4-dialkylphenylgroup, a 2,5-dialkylphenyl group, a 3,5-dialkylphenyl group, a2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively,a 2-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenyl group,a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group;alternatively, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenylgroup; alternatively, a 2-alkylphenyl group; alternatively, a4-alkylphenyl group; alternatively, a 2,3-dialkylphenyl group;alternatively, a 2,4-dialkylphenyl group; alternatively, a2,5-dialkylphenyl group; alternatively, a 3,5-dialkylphenyl group;alternatively, a 2,6-dialkylphenyl group; or alternatively, a2,4,6-trialkylphenyl group. Generally, the alkyl substituents of adialkylphenyl group (general or specific) or a trialkylphenyl group(general or specific) can be the same; or alternatively, the alkylsubstituents of a dialkylphenyl group or trialkylphenyl group can bedifferent. Alkyl substituent groups (general and specific) areindependently described herein and these alkyl substituent groups can beutilized, without limitation, to further describe any alkyl substitutedphenyl group which can be utilized as the first imine nitrogen groupand/or the second imine nitrogen group. In some non-limiting aspects,the substituted phenyl groups which can be the first imine nitrogengroup and/or the second imine nitrogen group can be a 2,6-dimethylphenylgroup, a 2,6-diethylphenyl group, a 2,6-diisopropylphenyl group, or a2,5-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, a2,4,6-trimethylphenyl group, a 2,6-dimethyl-4-(tert-butyl)phenyl group,2,6-dimethyl-4-(2,2-dimethylbenzyl)phenyl group, a2,6-dimethyl-4-(1,1-diphenylethyl)phenyl group, or a2,6-dimethyl-4-(1,1,3,3-tetramethylbutyl)phenyl group; alternatively, a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, or a2,6-diisopropylphenyl group; alternatively, a 2,6-dimethylphenyl groupor a 2,4,6-trimethylphenyl group; alternatively, a 2,6-dimethylphenylgroup; alternatively, a 2,6-diethylphenyl group; alternatively, a2,6-diisopropylphenyl group; alternatively, a 2,5-di-tert-butylphenylgroup; alternatively, a 2-isopropyl-6-methylphenyl group; alternatively,a 2,4,6-trimethylphenyl group; or alternatively, a2,6-dimethyl-4-(1,1,3,3-tetramethylbutyl)phenyl group.

In tridentate α-diimine aspects, the second imine nitrogen group cancomprise (1) a metal salt complexing group (or the first metal saltcomplexing group for the α-diimine first metal salt complex) and (2) alinking group linking the metal salt complexing group (or the firstmetal salt complexing group for the α-diimine first metal salt complex)to a second imine nitrogen atom of the α-diimine group. Generally, themetal salt complexing group (or the first metal salt complexing groupfor the α-diimine first metal salt complex) and the linking grouplinking the metal salt complexing group (or the first metal saltcomplexing group for the α-diimine first metal salt complex) to thesecond imine nitrogen atom of the α-diimine group are independentelements of the second imine group and are independently describedherein. The independent descriptions of the metal salt complexing group(or the first metal salt complexing group for the α-diimine first metalsalt complex) and the linking group can be used without limitation, andin any combination, to further describe the second imine groupcomprising (1) a metal salt complexing group (or the first metal saltcomplexing group for the α-diimine first metal salt complex) and (2) alinking group linking the metal salt complexing group (e.g. the firstmetal salt complexing group for the α-diimine first metal salt complex)to a second imine nitrogen atom of the α-diimine group of an α-diimine.

Generally, the metal salt complexing group (or the first metal saltcomplexing group for the α-diimine first metal salt complex) can be anygroup comprising a heteroatom capable of complexing with the metal salt(or the first metal salt for the α-diimine first metal salt complex) andthe linking group can be any group capable of linking the metal saltcomplexing group (or the first metal salt complexing group for theα-diimine first metal salt complex) to the second imine nitrogen atom ofthe α-diimine group. The linking group includes all atoms between thesecond imine nitrogen atom and the metal salt complexing group (or thefirst metal salt complexing group for the α-diimine first metal saltcomplex). If the metal salt complexing group (or the first metal saltcomplexing group for the α-diimine first metal salt complex) is acyclic,the linking group includes all atoms between the second imine nitrogenatom and the heteroatom of the metal salt complexing (or the first metalsalt complexing group for the α-diimine first metal salt complex)functional group. For example, in an N,N′-dimethylethylene group, thelinking group is —CH₂CH₂— and the metal salt complexing group (or thefirst metal salt complexing group for the α-diimine first metal saltcomplex) is the N,N′-dimethylaminyl group, while in a 2-phenoxyethylgroup the linking group is —CH₂CH₂— and the metal salt complexing group(or the first metal salt complexing group for the α-diimine first metalsalt complex) is the phenoxy group. However, if the heteroatom of themetal salt complexing group (or the first metal salt complexing groupfor the α-diimine first metal salt complex) is contained within a ring,the linking group includes all the atoms between the second iminenitrogen atom and the first atom within the ring containing the metalsalt (or the first metal salt for the α-diimine first metal saltcomplex) complexing heteroatom of the metal salt complexing group (orthe first metal salt complexing group for the α-diimine first metal saltcomplex). For example, in a 2-ethylpyridinyl group the linking group is—CH₂CH₂— and the metal salt complexing group (or the first metal saltcomplexing group for the α-diimine first metal salt complex) is the2-pyridinyl group, while in 1-ethylpiperidinyl group the linking groupis —CH₂CH₂— and the metal salt complexing group (or the first metal saltcomplexing group for the α-diimine first metal salt complex) is the1-piperidinyl group.

The metal salt complexing group (or the first metal salt complexinggroup for the α-diimine first metal salt complex) can be any groupcomprising a heteroatom capable of complexing with the metal salt (orthe first metal salt for the α-diimine first metal salt complex). In anaspect, the metal salt complexing group (or the first metal saltcomplexing group for the α-diimine first metal salt complex) can be a C₂to C₃₀ group comprising a heteroatom, a C₂ to C₂₀ group comprising aheteroatom, a C₂ to C₁₀ group comprising a heteroatom, or a C₂ to C₅group comprising a heteroatom wherein the heteroatom is capable ofcomplexing with the metal salt (or the first metal salt for theα-diimine first metal salt complex). In some aspects, the metal saltcomplexing heteroatom (or the first metal salt complexing heteroatom forthe α-diimine first metal salt complex) of the metal salt complexinggroup (or the first metal salt complexing group for the α-diimine firstmetal salt complex) can be an oxygen, sulfur, nitrogen, or phosphorus;alternatively, oxygen or sulfur, or alternatively, nitrogen orphosphorus. In other aspects, the metal salt complexing heteroatom (orthe first metal salt complexing heteroatom for the α-diimine first metalsalt complex) of the metal salt complexing group (or the first metalsalt complexing group for the α-diimine first metal salt complex) can beoxygen; alternatively, sulfur, alternatively, nitrogen; oralternatively, phosphorus. Optionally, the metal salt complexing group(or the first metal salt complexing group for the α-diimine first metalsalt complex) can contain additional heteroatoms which do not complexthe metal salt (or the first metal salt for the α-diimine first metalsalt complex) in the α-diimine metal salt complex (or the α-diiminefirst metal salt complex) such as inert heteroatoms (e.g. halides andsilicon) and/or additional metal salt complexing heteroatom(s) (or thefirst metal salt complexing heteroatom(s) for the α-diimine first metalsalt complex) which do not complex with the metal salt (or the firstmetal salt for the α-diimine first metal salt complex).

In an aspect, the metal salt complexing group (or the first metal saltcomplexing group for the α-diimine first metal salt complex) can be adihydrocarbyl aminyl group, a di(substituted hydrocarbyl) aminyl group,a dihydrocarbyl phosphinyl group, a di(substituted hydrocarbyl)phosphinyl group, a hydrocarbyl etheryl group, a substituted hydrocarbyletheryl group, a hydrocarbyl sulfidyl group, a substituted hydrocarbylsulfidyl group, a furanyl group, a substituted furanyl group, atetrahydrofuranyl group, a substituted tetrahydrofuranyl group, apyridinyl group, a substituted pyridinyl group, a morphilinyl group, asubstituted morphilinyl group, a pyrrolyl group, a substituted pyrrolylgroup, a pyrrolidinyl group, a substituted pyrrolidinyl group, apiperidinyl group, or a substituted piperidinyl group. In some aspects,the metal salt complexing group (or the first metal salt for theα-diimine first metal salt complex) can be a dihydrocarbyl aminyl groupor a di(substituted hydrocarbyl) aminyl group; alternatively, adihydrocarbyl phosphinyl group or a di(substituted hydrocarbyl)phosphinyl group; alternatively, a hydrocarbyl etheryl group or asubstituted hydrocarbyl etheryl group; or alternatively, a hydrocarbylsulfidyl group or a hydrocarbyl sulfidyl group. In other aspects, themetal salt complexing group (or the first metal salt complexing groupfor the α-diimine first metal salt complex) can be a dihydrocarbylaminyl group; alternatively, a di(substituted hydrocarbyl) aminyl group;alternatively, a dihydrocarbyl phosphinyl group; or alternatively, adi(substituted hydrocarbyl) phosphinyl group. Each substituent of asubstituted metal salt complexing group (or a first metal saltcomplexing group for the α-diimine first metal salt complex)independently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. Substituenthalogens, substituent hydrocarbyl groups (general and specific), andsubstituent hydrocarboxy groups (general and specific) are independentlydisclosed herein. These substituent halogens, substituent hydrocarbylgroups, and substituent hydrocarboxy groups can be utilized withoutlimitation to further describe a substituted metal salt complexing group(or a substituted first metal salt complexing group for the α-diiminefirst metal salt complex).

Each hydrocarbyl group of any metal salt complexing group (or any firstmetal salt complexing group for the α-diimine first metal salt complex)having a hydrocarbyl group disclosed herein independently can be a C₁ toC₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ hydrocarbyl group whileeach substituted hydrocarbyl group of a metal salt complexing group (ora first metal salt complexing group for the α-diimine first metal saltcomplex) having a substituted hydrocarbyl group disclosed hereinindependently can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ toC₅ substituted hydrocarbyl group. In an aspect, eachhydrocarbyl/substituted hydrocarbyl group of a metal salt complexinggroup (or the first metal salt complexing group for the α-diimine firstmetal salt complex) having a hydrocarbyl/substituted hydrocarbyl groupdescribed herein independently can be an alkyl group, a substitutedalkyl group, a cycloalkyl group, a substituted cycloalkyl group, an arylgroup, or a substituted aryl group; alternatively, an alkyl group or asubstituted alkyl group; alternatively, a cycloalkyl group or asubstituted cycloalkyl group; alternatively, an aryl group or asubstituted aryl group; alternatively, an alkyl group, a cycloalkylgroup, or an aryl group; alternatively, an alkyl group; alternatively, asubstituted alkyl group, alternatively, a cycloalkyl group;alternatively, a substituted cycloalkyl group; alternatively, an arylgroup; or alternatively, a substituted aryl group. Each substituent of asubstituted alkyl group (general or specific), a substituted cycloalkylgroup (general or specific), a substituted aryl group (general orspecific), and/or a substituted aralkyl group (general or specific) canbe a halogen, a hydrocarbyl group, or a hydrocarboxy group;alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. Substituenthalogens, substituent hydrocarbyl groups (general and specific), andsubstituent hydrocarboxy groups (general and specific) are independentlydisclosed herein. These substituent halogens, substituent hydrocarbylgroups, and substituent hydrocarboxy groups can be utilized withoutlimitation to further describe a substituted metal salt complexing group(or the substituted first metal salt complexing group for the α-diiminefirst metal salt complex).

In any aspect and/or embodiment disclosed herein, the alkyl group of anymetal salt complexing group (or the first metal salt complexing groupfor the α-diimine first metal salt complex) having an alkyl groupdisclosed herein independently can be a C₁ to C₂₀, a C₁ to C₁₀, or a C₁to C₅ alkyl group while the substituted alkyl group of any metal saltcomplexing group (or any first metal salt complexing group for theα-diimine first metal salt complex) having a substituted alkyl groupdisclosed herein independently can be a C₁ to C₂₀, a C₁ to C₁₀, or a C₁to C₅ substituted alkyl group. In an aspect, the alkyl group of anymetal salt complexing group (or the first metal salt complexing groupfor the α-diimine first metal salt complex) having an alkyl groupdisclosed herein independently can be a methyl group, an ethyl group, apropyl group, a butyl group, or a pentyl group. In some aspects, thealkyl group of any metal salt complexing group (or the first metal saltcomplexing group for the α-diimine first metal salt complex) having analkyl group disclosed herein independently can be a methyl group, anethyl group, an n-propyl group, an isopropyl group, an n-butyl group, asec-butyl group, an isobutyl group, a tert-butyl group, an n-pentylgroup, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, atert-pentyl group, a 3-methyl-1-butyl group, a 3-methyl-2-butyl group,or a neo-pentyl group. In some aspects, the alkyl groups which can beutilized as the alkyl group of any metal salt complexing group (or anyfirst metal salt complexing group for the α-diimine first metal saltcomplex) having an alkyl group disclosed herein can be substituted. Eachsubstituent of a substituted alkyl group (general or specific)independently can be a halogen or a hydrocarboxy group; alternatively, ahalogen; or alternatively, a hydrocarboxy group. Substituent halogensand substituent hydrocarboxy groups (general and specific) areindependently disclosed herein. These substituent halogens andsubstituent hydrocarboxy groups can be utilized without limitation tofurther describe a substituted alkyl group which can be utilized as thesubstituted alkyl group of a metal salt complexing group (or a firstmetal salt complexing group for the α-diimine first metal salt complex).

In any aspect or embodiment disclosed herein, the cycloalkyl group ofany metal salt complexing group (or any first metal salt complexinggroup for the α-diimine first metal salt complex) having a cycloalkylgroup disclosed herein independently can be a C₄ to C₂₀, a C₄ to C₁₅, ora C₄ to C₁₀ cycloalkyl group while the substituted cycloalkyl group ofany metal salt complexing group (or any first metal salt complexinggroup for the α-diimine first metal salt complex) having a substitutedcycloalkyl group disclosed herein independently can be a C₄ to C₂₀, a C₄to C₁₅, or a C₄ to C₁₀ substituted cycloalkyl group. In an aspect, eachcycloalkyl/substituted cycloalkyl group of a metal salt complexing group(or a first metal salt complexing group for the α-diimine first metalsalt complex) having a cycloalkyl/substituted cycloalkyl group describedherein independently can be cyclopentyl group, a substituted cyclopentylgroup, a cyclohexyl group, or a substituted cyclohexyl group;alternatively, a cyclopentyl group or a substituted cyclopentyl group;alternatively, a cyclohexyl group or a substituted cyclohexyl group;alternatively, a cyclopentyl group; alternatively, a substitutedcyclopentyl group; alternatively, a cyclohexyl group; or alternatively,a substituted cyclohexyl group. Each substituent of a substitutedcycloalkyl group having a specified number of ring carbon atomsindependently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen, alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. Substituenthalogens, substituent hydrocarbyl groups (general and specific), andsubstituent hydrocarboxy (general and specific) groups are independentlydisclosed herein. These substituent halogens, substituent hydrocarbylgroups, and substituent hydrocarboxy groups can be utilized withoutlimitation to further describe a substituted cycloalkyl group which canbe utilized as the substituted cycloalkyl group of a metal saltcomplexing group (or a first metal salt complexing group for theα-diimine first metal salt complex).

In any aspect and/or embodiment disclosed herein, the aryl group of anymetal salt complexing group (or any first metal salt complexing groupfor the α-diimine first metal salt complex) having an aryl groupdisclosed herein independently can be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆to C₁₀ aryl group while the substituted aryl group of any metal saltcomplexing group (or any first metal salt complexing group for theα-diimine first metal salt complex) having a substituted aryl groupdisclosed herein independently a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀substituted aryl group. In an aspect, the aryl/substituted aryl group ofany metal salt complexing group (or any first metal salt complexinggroup for the α-diimine first metal salt complex) having anaryl/substituted aryl group disclosed herein independently can be aphenyl group or a substituted phenyl group; alternatively, a phenylgroup; or alternatively, a substituted phenyl group. In some aspects,the substituted phenyl group of any metal salt complexing group (or anyfirst metal salt complexing group for the α-diimine first metal saltcomplex) having a substituted phenyl group independently can be a C₆ toC₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ substituted phenyl group. In someaspects, the substituted phenyl group of any metal salt complexing group(or any first metal salt complexing group for the α-diimine first metalsalt complex) having a substituted phenyl group independently can be a2-substituted phenyl group, a 3-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2-substituted phenylgroup, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group,or a 2,6-disubstituted phenyl group; alternatively, a 3-substitutedphenyl group or a 3,5-disubstituted phenyl group; alternatively, a2-substituted phenyl group or a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group or a 2,6-disubstitutedphenyl group; alternatively, a 2-substituted phenyl group;alternatively, a 3-substituted phenyl group; alternatively, a4-substituted phenyl group; alternatively, a 2,4-disubstituted phenylgroup; alternatively, a 2,6-disubstituted phenyl group; alternatively, a3,5-disubstituted phenyl group; or alternatively, a 2,4,6-trisubstitutedphenyl group. In an aspect, one or more substituents of amulti-substituted phenyl group utilized as a substituted phenyl groupfor any metal salt complexing group (or any first metal salt complexinggroup for the α-diimine first metal salt complex) having a substitutedaryl group or substituted phenyl group described herein can be the sameor different; alternatively, all the substituents of a multi-substitutedcycloalkyl group can be the same; or alternatively, all the substituentsof a multi-substituted cycloalkyl group can be different. Eachsubstituent of a substituted aryl group (general or specific) orsubstituted phenyl group (general or specific) which can be utilized asa substituted aryl group or a substituted phenyl group for any metalsalt complexing group (or any first metal salt complexing group for theα-diimine first metal salt complex) having a substituted aryl group orsubstituted phenyl group independently can be a halogen, a hydrocarbylgroup, or a hydrocarboxy group; alternatively, a halogen or ahydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen, alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe a substituted aryl group (general or specific) or a substitutedphenyl group (general or specific) which can be utilized as utilized asa substituted aryl group or a substituted phenyl group for any metalsalt complexing group (or any first metal salt complexing group for theα-diimine first metal salt complex) having a substituted aryl group orsubstituted phenyl group.

In an aspect, the substituted phenyl group of any metal salt complexinggroup (or any first metal salt complexing group for the α-diimine firstmetal salt complex) having a substituted phenyl group disclosed hereinindependently can be a 2-alkylphenyl group, a 3-alkylphenyl group, a4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenylgroup, a 3,5-dialkylphenyl group, or a 2,4,6-trialkylphenyl group;alternatively, a 2-alkylphenyl group, a 4-alkylphenyl group, a2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, or a2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group or a4-alkylphenyl group; alternatively, a 2,4-dialkylphenyl group, or a2,6-dialkylphenyl group; alternatively, a 3-alkylphenyl group or a3,5-dialkylphenyl group; alternatively, a 2-alkylphenyl group or a2,6-dialkylphenyl group; alternatively, a 2-alkylphenyl group;alternatively, a 4-alkylphenyl group; alternatively, a 2,4-dialkylphenylgroup; alternatively, a 2,6-dialkylphenyl group; or alternatively, a2,4,6-trialkylphenyl group. In an embodiment, one or more alkyl groupsubstituents of a multi-alkyl group substituted phenyl group utilized asa substituted phenyl group for any metal salt complexing group (or anyfirst metal salt complexing group for the α-diimine first metal saltcomplex) having an alkyl substituted phenyl group described herein canbe the same or different; alternatively, all the substituents of amulti-alkyl group substituted cycloalkyl group can be the same; oralternatively, all the substituents of a multi-alkyl group substitutedcycloalkyl group can be different. Alkyl substituent groups (general andspecific) are independently described herein and these alkyl substituentgroups can be utilized, without limitation, to further describe anyalkyl substituted phenyl group which can be utilized as a substitutedphenyl group for any metal salt complexing group (or any first metalsalt complexing group for the α-diimine first metal salt complex) havinga substituted aryl group or substituted phenyl group described herein.Generally, the alkyl substituents of a dialkylphenyl group (general orspecific) or a trialkylphenyl group (general or specific) can be thesame; or alternatively, the alkyl substituents of a dialkylphenyl group(general or specific) or a trialkyl phenyl group (general or specific)can be different. In some non-limiting aspects, the substituted phenylgroup of any metal salt complexing group (or any first metal saltcomplexing group for the α-diimine first metal salt complex) having asubstituted phenyl group disclosed herein independently can be a3,5-dimethylphenyl group.

The linking group linking the metal salt complexing group (or the firstmetal salt complexing group for the α-diimine first metal salt complex)to the second imine nitrogen atom of the α-diimine group can be a bondor an organyl group; alternatively, a bond or an organyl groupconsisting essentially of inert functional groups; alternatively, a bondor a hydrocarbyl group; alternatively, an organyl group; alternatively,an organyl group consisting essentially of inert functional groups;alternatively, a hydrocarbyl group; or alternatively, a bond. In anyaspect and/or embodiment disclosed herein, the organyl linking grouplinking the metal salt complexing group (or the first metal saltcomplexing group for the α-diimine first metal salt complex) to thesecond imine nitrogen atom of the α-diimine group can be a C₁ to C₂₀, aC₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl group. In any aspectand/or embodiment disclosed herein, the organyl group consistingessentially of inert functional groups linking group linking the metalsalt complexing group (or the first metal salt complexing group for theα-diimine first metal salt complex) to the second imine nitrogen atom ofthe α-diimine group can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or aC₁ to C₅ organyl group consisting essentially of inert functionalgroups. In any aspect and/or embodiment disclosed herein, thehydrocarbyl group linking group linking the metal salt complexing group(or the first metal salt complexing group for the α-diimine first metalsalt complex) to the second imine nitrogen atom of the α-diimine groupcan be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ hydrocarbylgroup. In any aspect and/or embodiment disclosed herein, the hydrocarbylgroup linking group linking the metal salt complexing group (or thefirst metal salt complexing group for the α-diimine first metal saltcomplex) to the second imine nitrogen atom of the α-diimine group can bea C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ alkyl group.Generally, the linking group linking the metal salt complexing group (orthe first metal salt complexing group for the α-diimine first metal saltcomplex) to the second imine nitrogen atom of the α-diimine group can besaturated or unsaturated, linear or branched, acyclic or cyclic, and/oraliphatic or aromatic.

In an aspect, the linking group linking the metal salt complexing group(or the first metal salt complexing group for the α-diimine first metalsalt complex) to the second imine nitrogen atom of the α-diimine groupcan be —(C(R^(L1))₂)—, a phenyl-1,2-ene group, or a substitutedphenyl-1,2-ene group; alternatively, a phenyl-1,2-ene group or asubstituted phenyl-1,2-ene group; alternatively, —(C(R^(L1))₂)—;alternatively, a phenyl-1,2-ene group; alternatively, a substitutedphenyl-1,2-ene group. R^(L1) and m are independent elements of thelinking group having the structure —(C(R^(L1))₂)— and are independentlydescribed herein. The independent descriptions of R^(L) and m can beutilized without limitation, and in any combination, to further describethe linking group linking the metal salt complexing group (or the firstmetal salt complexing group for the α-diimine first metal salt complex)to the second imine nitrogen atom of the α-diimine group having thestructure —(C(R^(L1))₂)—. Within the structure —(C(R^(L1))₂)_(m)—, eachR^(L1) independently can be hydrogen, a methyl group, an ethyl group, apropyl group, an isopropyl group, or a butyl group; alternatively,hydrogen, a methyl group, or a propyl group. Within the structure—(C(R^(L1))₂)—, m can be an integer from 1 to 5; alternatively, 2 or 3;alternatively, 2; or alternatively, 3. Each substituent of a substitutedphenyl-1,2-ene group which can be utilized as the linking group linkingthe metal salt complexing group (or the first metal salt complexinggroup for the α-diimine first metal salt complex) to the second iminenitrogen atom of the α-diimine group can be a halide, an alkyl group, oran alkoxy group; alternatively, a halide or an alkyl group;alternatively, a halide and an alkoxy group; alternatively, an alkylgroup or an alkoxy group; alternatively, a halide; alternatively, analkyl group; or alternatively, an alkoxy group. Halides, alkyl groups(general and specific), and alkoxy groups (general and specific) thatcan be utilized as substituents are independently disclosed herein andcan be utilized without limitation, and in any combination, to furtherdescribe the substituted phenyl-1,2-ene group which can be utilized asthe linking group linking the metal salt complexing group (or the firstmetal salt complexing group for the α-diimine first metal salt complex)to the second imine nitrogen atom of the α-diimine group. In someaspects, the linking group linking the metal salt complexing group (orthe first metal salt complexing group for the α-diimine first metal saltcomplex) to the second imine nitrogen atom of the α-diimine group can bea methylene group, an eth-1,2-ylene group, a prop-1,3-ylene group, adimethylmethylene group, a butyl-1,4-ene group or a phen-1,2-ylenegroup. In some non-limiting aspects, the linking group linking the metalsalt complexing group (or the first metal salt complexing group for theα-diimine first metal salt complex) to the second imine nitrogen atom ofthe α-diimine group can be an eth-1,2-ylene group, a prop-1,3-ylenegroup, or a phen-1,2-ylene group; alternatively, an eth-1,2-ylene group,or a prop-1,3-ylene group; alternatively, an eth-1,2-ylene group;alternatively, a prop-1,3-ylene group; or alternatively, aphen-1,2-ylene group.

In a non-limiting aspect, the second imine group comprising (1) a metalsalt complexing group (or the first metal salt complexing group for theα-diimine first metal salt complex) and (2) a linking group linking themetal salt complexing group (or the first metal salt complexing groupfor the α-diimine first metal salt complex) to a second imine nitrogenatom of the α-diimine group can be a 2-(N,N′-diisopropylaminyl)ethylgroup, a 2-(N,N′-diphenylaminyl)ethyl group, a2-(N,N′-di-(3,5-dimethylphenyl)aminyl)ethyl group, a2-(diisopropylphosphinyl)ethyl group, a 2-(diphenylphosphinyl)ethylgroup, a 2-(di-(3,5-dimethylphenyl)phosphinyl)ethyl group, a3-(diisopropylphosphinyl)propyl group, a 3-(diphenylphosphinyl)propylgroup, a 3-(di-(3,5-dimethylphenyl)phosphinyl)propyl group, a2-isopropoxyethyl group, a 2-phenoxyethyl group, or a2-(3,5-dimethylphenoxy)ethyl group. In some non-limiting aspects, thesecond imine group comprising (1) a metal salt complexing group (or thefirst metal salt complexing group for the α-diimine first metal saltcomplex) and (2) a linking group linking the metal salt complexing group(or the first metal salt complexing group for the α-diimine first metalsalt complex) to a second imine nitrogen atom of the α-diimine group canbe a 2-(N,N′-diisopropylaminyl)ethyl group, a2-(N,N′-diphenylaminyl)ethyl group, a2-(N,N′-di-(3,5-dimethylphenyl)aminyl)ethyl group; alternatively, a2-(diisopropylphosphinyl)ethyl group, a 2-(diphenylphosphinyl)ethylgroup, a 2-(di-(3,5-dimethylphenyl)phosphinyl)ethyl group, a3-(diisopropylphosphinyl)propyl group, a 3-(diphenylphosphinyl)propylgroup, a 3-(di-(3,5-dimethylphenyl)phosphinyl)propyl group; oralternatively, a 2-isopropoxyethyl group, a 2-phenoxyethyl group, or a2-(3,5-dimethylphenoxy)ethyl group. In other non-limiting aspects, thesecond imine group comprising (1) a metal salt complexing group (e.g.the first metal salt complexing group for the α-diimine first metal saltcomplex) and (2) a linking group linking the metal salt complexing group(e.g. the first metal salt complexing group for the α-diimine firstmetal salt complex) to a second imine nitrogen atom of the α-diiminegroup can be a 2-(diisopropylphosphinyl)ethyl group, a2-(diphenylphosphinyl)ethyl group, a2-(di-(3,5-dimethylphenyl)phosphinyl)ethyl group; alternatively, a3-(diisopropyl-phosphinyl)propyl group, a 3-(diphenylphosphinyl)propylgroup, a 3-(di-(3,5-dimethylphenyl)-phosphinyl)propyl group;alternatively, a 2-(diisopropylphosphinyl)ethyl group; alternatively, a2-(diphenylphosphinyl)ethyl group; or alternatively, a2-(di-(3,5-dimethylphenyl)phosphinyl)ethyl group.

In various aspects and/or embodiments, a pyridine bisimine and a metalsalt, or a pyridine bisimine first metal salt complex, can be utilizedin the processes described herein. Generally, the pyridine bisimine orthe pyridine bisimine of the pyridine bisimine first metal salt complexdisclosed herein, can be any pyridine bisimine, or any pyridine bisimineof the pyridine bisimine first metal salt complex disclosed herein, thatwhen contacted with the other materials of the process described herein(e.g., metal salt, ethylene, organoaluminum compound and/or any otherappropriate reagent(s)), under the appropriate conditions, can form anoligomer product. Generally, the pyridine bisimine and the metal salt,or pyridine bisimine first metal salt complexes (or the pyridinebisimine and the first metal salt of the pyridine bisimine first metalsalt complex) are independent elements of the processes described hereinand are independently disclosed herein. The independent descriptions ofthe pyridine bisimine and the metal salt, or pyridine bisimine firstmetal salt complexes (or the pyridine bisimine and the first metal saltof the pyridine bisimine first metal salt complex) can be used withoutlimitation, and in any combination, to further describe the processesthat can be utilized in the aspects and/or embodiments of the processesdescribed herein. In an aspect, the pyridine bisimine (or the pyridinebisimine of the pyridine bisimine first metal salt complex) can compriseonly one pyridine bisimine group; alternatively, at least two pyridinebisimine groups; or alternatively, the pyridine bisimine can compriseonly two pyridine bisimine groups.

In an aspect, the pyridine bisimine or the pyridine bisimine of thepyridine bisimine first metal salt complex can have Structure PBI I orStructure PBI II; alternatively, Structure PBI I; or alternatively,Structure PBI II. In an aspect, any pyridine bisimine first metal saltcomplex can have Structure PBIMC I or Structure PBIMC II; alternatively,Structure PBIMC I; or alternatively, Structure PBIMC II.

R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ of the pyridine bisimine having StructurePBI I or the pyridine bisimine first metal salt complex having StructurePBIMC I are independent elements of the pyridine bisimine havingStructure PBI I and the pyridine bisimine first metal salt complexhaving Structure PBIMC I and are independently described herein. Theindependent descriptions of R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ can utilizedwithout limitation, and in any combination, to further describe thepyridine bisimine having Structure PBI I and/or the pyridine bisiminefirst metal salt complex having Structure PBIMC I. Similarly, R², R⁶,R⁷, L¹, and L² of the pyridine bisimine having Structure PBI II or thepyridine bisimine first metal salt complex having Structure PBIMC II areindependent elements of the pyridine bisimine having Structure PBI IIand the pyridine bisimine first metal salt complex having StructurePBIMC II and are independently described herein. The independentdescriptions of R², R⁶, R⁷, L¹, and L² can utilized without limitation,and in any combination, to further describe the pyridine bisimine havingStructure PBI II and/or the pyridine bisimine first metal salt complexhaving Structure PBIMC II. Additionally, the first metal salt, MX_(n),is independently described herein and can be combined, withoutlimitation, with the independently described R¹, R², R³, R⁴, R⁵, R⁶, R⁷,L¹, and L² to further describe the appropriate pyridine bisimine firstmetal salt complex structure described herein which have an R¹, R², R³,R⁴, R⁵, R⁶, R⁷, L¹, and/or L².

Generally, R¹, R², and/or R³ of the respective pyridine bisimines andpyridine bisimine first metal salt complexes, which have an R¹, R²,and/or R³, independently can be hydrogen, an inert functional group, oran organyl group; alternatively, hydrogen or an organyl group;alternatively, an inert functional group or an organyl group;alternatively, hydrogen, an inert functional group, or an organyl groupconsisting essentially of inert functional groups; alternatively,hydrogen or an organyl group consisting essentially of inert functionalgroups; alternatively, an inert functional group or an organyl groupconsisting essentially of inert functional groups; alternatively,hydrogen, an inert functional group, or a hydrocarbyl group;alternatively, hydrogen or a hydrocarbyl group; alternatively, an inertfunctional group or a hydrocarbyl group; alternatively, hydrogen or aninert functional group; alternatively, hydrogen; alternatively, an inertfunctional group; alternatively, an organyl group; alternatively,organyl group consisting essentially of inert functional groups; oralternatively, a hydrocarbyl group. In any aspect and/or embodimentdisclosed herein, the R¹, R², and/or R³ organyl groups of the pyridinebisimines and/or pyridine bisimine first metal salt complexes which havean R¹, R², and/or R³ group, independently can be a C₁ to C₂₀, a C₁ toC₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl group. In any aspect and/orembodiment disclosed herein, the R¹, R², and/or R³ organyl groupsconsisting essentially of inert functional groups, of the pyridinebisimines and/or pyridine bisimine first metal salt complexes which havean R¹, R², and/or R³ group, independently can be a C₁ to C₂₀, a C₁ toC₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl group consisting essentially ofinert functional groups. In any aspect and/or embodiment disclosedherein, the R¹, R², and/or R³ hydrocarbyl groups of the pyridinebisimines and/or pyridine bisimine first metal salt complexes which havean R¹, R², and/or R³ group, independently can be a C₁ to C₂₀, a C₁ toC₁₅, a C₁ to C₁₀, or a C₁ to C₅ hydrocarbyl group.

In any aspect and/or embodiment disclosed herein, the hydrocarbyl groupwhich can be utilized as R¹, R², and/or R³ of the pyridine bisimines andpyridine bisimine first metal salt complexes which have an R¹, R²,and/or R³ hydrocarbyl group, independently can be a C₁ to C₂₀, a C₁ toC₁₀, or a C₁ to C₅ alkyl group. In an aspect, the R¹, R², and/or R³alkyl groups of the pyridine bisimines and pyridine bisimine first metalsalt complexes which have an R¹, R², and/or R³ alkyl group,independently can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, or an octylgroup. In some aspects, the R¹, R², and/or R³ alkyl groups of thepyridine bisimines and pyridine bisimine first metal salt complexeswhich have an R¹, R², and/or R³ alkyl group, independently can be amethyl group, an ethyl group, an iso-propyl (2-propyl) group, atert-butyl (2-methyl-2-propyl) group, or a neopentyl(2,2-dimethyl-1-propyl) group; alternatively, a methyl group;alternatively, an ethyl group; alternatively, a n-propyl (1-propyl)group; alternatively, an iso-propyl (2-propyl) group; alternatively, atert-butyl (2-methyl-2-propyl) group; or alternatively, a neopentyl(2,2-dimethyl-1-propyl) group.

In a particular aspect, R¹, R², and/or R³ of the pyridine bisimineswhich have an R¹, R², and/or R³ group, each can be hydrogen. In theseaspects, the pyridine bisimine can have Structure PBI III or StructurePBI IV; alternatively, Structure PBI III; or alternatively, StructurePBI IV. Similarly, in a particular aspect, R¹, R², and R³ of thepyridine bisimine first metal salt complexes which have an R¹, R²,and/or R³ group, each can be hydrogen. In these aspects, the pyridinebisimine first metal salt complexes can have Structure PBIMC III orStructure PBIMC IV; alternatively, Structure PBIMC III; oralternatively, Structure PBIMC IV.

R⁴, R⁵, R⁶, and R⁷ of the pyridine bisimine having Structure PBI III orthe pyridine bisimine first metal salt complex having Structure PBIMCIII are independent elements of the pyridine bisimine having StructurePBI III and the pyridine bisimine first metal salt complex havingStructure PBIMC III and are independently described herein. Theindependent descriptions of R⁴, R⁵, R⁶, and R⁷ can be utilized withoutlimitation, and in any combination, to further describe the pyridinebisimine having Structure PBI III and/or the pyridine bisimine firstmetal salt complex having Structure PBIMC III. Similarly, R⁶, R⁷, L¹,and L² of the pyridine bisimine having Structure PBI IV or the pyridinebisimine first metal salt complex having Structure PBIMC IV areindependent elements of the pyridine bisimine having Structure PBI IVand the pyridine bisimine first metal salt complex having StructurePBIMC IV and are independently described herein. The independentdescriptions of R⁶, R⁷, L¹, and L² can be utilized without limitation,and in any combination, to further describe the pyridine bisimine havingStructure PBI IV and/or the pyridine bisimine first metal salt complexhaving Structure PBIMC IV. Additionally, the first metal salt, MX_(n),is independently described herein and can be combined, withoutlimitation, with the independently described R⁴, R⁵, R⁶, R⁷, L¹, and L²to further describe the appropriate pyridine bisimine first metal saltcomplex structure described herein which have an R⁴, R⁵, R⁶, R⁷, L¹,and/or L².

Generally, R⁴ and/or R⁵ of the pyridine bisimines and pyridine bisiminefirst metal salt complexes, which have an R⁴ and/or R⁵, independentlycan be hydrogen or an organyl group; alternatively, hydrogen or anorganyl group consisting essentially of inert functional groups;alternatively, hydrogen or a hydrocarbyl group; alternatively, hydrogen;alternatively, an organyl group; alternatively, an organyl groupconsisting essentially of inert functional groups; or alternatively, ahydrocarbyl group. In any aspect and/or embodiment disclosed herein, theR⁴ and/or R⁵ organyl groups of the pyridine bisimines and pyridinebisimine first metal salt complexes which have an R⁴ and/or R⁵ group,independently can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ toC₅ organyl group. In any aspect and/or embodiment disclosed herein, theR⁴ and/or R⁵ organyl groups consisting essentially of inert functionalgroups, of the pyridine bisimines and pyridine bisimine first metal saltcomplexes which have an R⁴ and/or R⁵ group, independently can be a C₁ toC₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl group consistingessentially of inert functional groups. In any aspect and/or embodimentdisclosed herein, the R⁴ and/or R⁵ hydrocarbyl groups of the pyridinebisimines and pyridine bisimine first metal salt complexes which have anR⁴ and/or R⁵ group, independently can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁to C₁₀, or a C₁ to C₅ hydrocarbyl group.

In any aspect and/or embodiment disclosed herein, the R⁴ and/or R⁵hydrocarbyl groups of the pyridine bisimines and pyridine bisimine firstmetal salt complexes which have an R⁴ and/or R⁵ group, independently canbe a C₁ to C₂₀, a C₁ to C₁₀, or a C₁ to C₅ alkyl group. In an aspect,the R⁴ and/or R⁵ alkyl groups of the pyridine bisimines and pyridinebisimine first metal salt complexes which have an R⁴ and/or R⁵ group,independently can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, or an octylgroup. In some aspects, the R⁴ and/or R⁵ alkyl groups of the pyridinebisimines and pyridine bisimine first metal salt complexes which have anR⁴ and/or R⁵ group, independently can be a methyl group, an ethyl group,an iso-propyl (2-propyl) group, a tert-butyl (2-methyl-2-propyl) group,or a neopentyl (2,2-dimethyl-1-propyl) group; alternatively, a methylgroup; alternatively, an ethyl group; alternatively, a n-propyl(1-propyl) group; alternatively, an iso-propyl (2-propyl) group;alternatively, a tert-butyl (2-methyl-2-propyl) group; or alternatively,a neopentyl (2,2-dimethyl-1-propyl) group.

In an aspect, R¹ and R⁴ and/or R³ and R⁵ can be joined to form a ring ora ring system containing two carbon atoms of the pyridine group and thecarbon atom of the imine group. In such aspects, L¹ represents thejoined R³ and R⁵ while L² represents the joined R¹ and R⁴. Generally, L¹and/or L² of a pyridine bisimine or pyridine bisimine metal salt complexhaving an L¹ and/or L² independently can be an organylene group;alternatively, an organylene group consisting essentially of inertfunctional groups; or alternatively, a hydrocarbylene group. In anyaspect or embodiment disclosed herein, the L¹ and/or L² organylenegroups of a pyridine bisimine or pyridine bisimine first metal saltcomplex which have an L¹ and/or L² group, independently can be a C₂ toC₂₀, a C₂ to C₁₅, a C₂ to C₁₀, or a C₂ to C₅ organylene group. In anyaspect or embodiment disclosed herein, the L¹ and/or L² organylenegroups consisting essentially of inert functional groups of a pyridinebisimine or pyridine bisimine first metal salt complex which have an L¹and/or L² group, independently can be a C₂ to C₂₀, a C₂ to C₁₅, a C₂ toC₁₀, or a C₂ to C₅ organylene group consisting essentially of inertfunctional groups. In any aspect or embodiment disclosed herein, the L¹and/or L² hydrocarbylene groups of a pyridine bisimine or pyridinebisimine first metal salt complex which have an L¹ and/or L² group,independently can be a C₂ to C₂₀, a C₂ to C₁₅, a C₂ to C₁₀, or a C₂ toC₅ hydrocarbylene group. In any aspect or embodiments disclosed herein,the L¹ and/or L² hydrocarbylene groups of the pyridine bisimines andpyridine bisimine first metal salt complexes which have an L¹ and/or L²,independently can be a C₂ to C₂₀, a C₂ to C₁₀, or a C₂ to C₅ alkylenegroup. In any aspect or embodiment where the pyridine bisimine or thepyridine bisimine first metal salt complex has an L¹ and an L² group, L¹and L² can be different; or alternatively, L¹ and L² can be the same.

In an embodiment, L¹ and/or L² independently can have the structure—(C(R¹¹)₂)_(p)—. Generally, R¹¹ and p are independent features of L¹and/or L² having the structure —(C(R¹¹)₂)_(p)— and are independentlydescribed herein. The independent descriptions of R¹¹ and p can beutilized without limitation, and in any combination, to describe L¹and/or L² having the structure —(C(R¹¹)₂)_(p)— and can be furtherutilized to describe the pyridine bisimines and/or the pyridine bisiminefirst metal salt complexes which have an L¹ and/or L². In an embodiment,each R¹¹ independently can be hydrogen, an inert functional group, or ahydrocarbyl group; alternatively, hydrogen or a hydrocarbyl group;alternatively, hydrogen; alternatively, an inert functional group; oralternatively, a hydrocarbyl group. General and specific inertfunctional groups and hydrocarbyl groups are independently describedherein (e.g., as potential substituent groups) and these descriptionscan be utilized without limitation to further describe L¹ and L². In anaspect, each p independently can be an integer from 1 to 5;alternatively, 2 or 3; alternatively, 2; or alternatively, 3. In anon-limiting aspect, L¹ and L² independently can be —CH₂CH₂—,—CH₂CH₂CH₂—, —C(CH₃)₂—, or —CH₂CH₂CH₂CH₂—; alternatively, —CH₂CH₂— or—CH₂CH₂CH₂—; alternatively, —CH₂CH₂—; or alternatively, —CHCH₂CH₂—. Inan aspect, L¹ and L² can be different. In other aspects, L¹ and L² canbe the same.

Generally, R⁶ and/or R⁷ of the pyridine bisimines and the pyridinebisimine first metal salt complexes independently can be an aryl group,a substituted aryl group, a phenyl group, or a substituted phenyl group;alternatively, an aryl group or a substituted aryl group; alternatively,a phenyl group or a substituted phenyl group; alternatively, an arylgroup; alternatively, a substituted aryl group; alternatively, a phenylgroup; or alternatively, a substituted phenyl group. In any aspectand/or embodiment disclosed herein, the R⁶ and/or R⁷ aryl groups of thepyridine bisimines and/or pyridine bisimine first metal salt complexesindependently can be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ arylgroup. In any aspect and/or embodiment disclosed herein, the R⁶ and/orR⁷ substituted aryl groups of the pyridine bisimines and/or pyridinebisimine first metal salt complexes independently can be a C₆ to C₂₀, aC₆ to C₁₅, or a C₆ to C₁₀ substituted aryl group. In any aspect and/orembodiment disclosed herein, the R⁶ and/or R⁷ substituted phenyl groupsof the pyridine bisimines and/or pyridine bisimine first metal saltcomplexes independently can be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₅substituted phenyl group. Each substituent of a substituted aryl group(general or specific) or a substituted phenyl group (general orspecific) which can be utilized as R⁶ and/or R⁷ can be a halide, analkyl group, or a hydrocarboxy group; alternatively, a halide or analkyl group; alternatively, a halide or a hydrocarboxy group;alternatively, an alkyl group or a hydrocarboxy group; alternatively, ahalide; alternatively, an alkyl group; or alternatively, a hydrocarboxygroup. Halides, alkyl groups (general and specific), and hydrocarboxygroups (general and specific) that can be utilized as substituents areindependently disclosed herein and can be utilized without limitation,and in any combination, to further describe R⁶ and/or R⁷ of the pyridinebisimines and the pyridine bisimine first metal salt complexes.

In an embodiment, each substituted phenyl group which can be utilized asR⁶ and/or R⁷ of the pyridine bisimines and the pyridine bisimine firstmetal salt complexes independently can be a substituted phenyl groupcomprising a substituent at the 2-position, a substituted phenyl groupcomprising a substituent at the 3-position, a substituted phenyl groupcomprising a substituent at the 4-position, a substituted phenyl groupcomprising substituents at the 2- and 3-positions, a substituted phenylgroup comprising substituents at the 2- and 4-positions, a substitutedphenyl group comprising substituents at the 2- and 5-positions, asubstituted phenyl group comprising substituents at the 3- and5-positions, a substituted phenyl group comprising substituents at the2- and 6-positions, or a substituted phenyl group comprisingsubstituents at the 2-, 4-, and 6-positions; alternatively, asubstituted phenyl group comprising a substituent at the 2-position, asubstituted phenyl group comprising a substituent at the 4-position, asubstituted phenyl group comprising substituents at the 2- and4-positions, a substituted phenyl group comprising substituents at the2- and 6-positions, or a substituted phenyl group comprisingsubstituents at the 2-, 4-, and 6-positions; alternatively, asubstituted phenyl group comprising substituents at the 2- and6-positions or a substituted phenyl group comprising substituents at the2-, 4-, and 6-positions; alternatively, a substituted phenyl groupcomprising a substituent at the 2-position; alternatively, a substitutedphenyl group comprising a substituent at the 3-position; alternatively,a substituted phenyl group comprising a substituent at the 4-position;alternatively, a substituted phenyl group comprising substituents at the2- and 3-positions; alternatively, a substituted phenyl group comprisingsubstituents at the 2- and 4-positions; alternatively, a substitutedphenyl group comprising substituents at the 2- and 5-positions;alternatively, a substituted phenyl group comprising substituents at the3- and 5-positions; alternatively, a substituted phenyl group comprisingsubstituents at the 2- and 6-positions; or alternatively, a substitutedphenyl group comprising substituents at the 2-, 4-, and 6-positions. Insome embodiments, each substituted phenyl group which can be utilized asR⁶ and/or R⁷ of the pyridine bisimines and the pyridine bisimine firstmetal salt complexes independently can be selected such that (1) one,two, or three of the 2- and 6-positions of the R⁶ and R⁷ phenyl groupsand/or substituted phenyl groups independently can be a halogen, aprimary carbon atom group, or a secondary carbon atom group and theremainder of the 2- and 6-positions of the R⁶ and R⁷ phenyl groupsand/or substituted phenyl groups can be hydrogen, (2) one of the 2- and6-positions of the R⁶ and R⁷ phenyl groups and/or substituted phenylgroups can be a tertiary carbon atom group, none, one, or two of the 2-and 6-positions of the R⁶ and R⁷ phenyl groups and/or substituted phenylgroups independently can be a halogen, a primary carbon atom group or asecondary carbon atom group, and the remainder of the 2- and 6-positionsof the R⁶ and R⁷ phenyl groups and/or substituted phenyl groups can behydrogen, (3) two of the 2- and 6-positions of the R⁶ and R⁷ phenylgroups and/or substituted phenyl groups can be a tertiary carbon atomgroup, none, or one of the 2- and 6-positions of the R⁶ and R⁷ phenylgroups and/or substituted phenyl groups independently can be a halogen,a primary carbon atom group, or a secondary carbon atom group, and theremainder of the 2- and 6-positions of the R⁶ and R⁷ phenyl groupsand/or substituted phenyl groups can be hydrogen, (4) one or two of the2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups can be a tertiary carbon atom group and the remainder ofthe 2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups can be hydrogen, 5) one or two of the 2- and 6-positionsof the R⁶ and R⁷ phenyl groups and/or substituted phenyl groups can be aquaternary carbon atom group and the remainder of the 2- and 6-positionsof the R⁶ and R⁷ phenyl groups and/or substituted phenyl groups can behydrogen, or 6) all four of the 2- and 6-positions of the R⁶ and R⁷substituted phenyl groups can be fluorine. Each substituent of asubstituted aryl group (general or specific) or a substituted phenylgroup (general or specific) which can be utilized as R⁶ and/or R⁷ can bea halide, an alkyl group, or a hydrocarboxy group; alternatively, ahalide or an alkyl group; alternatively, a halide or a hydrocarboxygroup; alternatively, an alkyl group or a hydrocarboxy group;alternatively, a halide; alternatively, an alkyl group; oralternatively, a hydrocarboxy group. Halides, alkyl groups (general andspecific), and hydrocarboxy groups (general and specific) that can beutilized as substituents are independently disclosed herein and can beutilized without limitation, and in any combination, to further describeR⁶ and/or R⁷ of the pyridine bisimines and the pyridine bisimine firstmetal salt complexes. Further, one having ordinary skill in the art canrecognize the independently described substituted phenyl group(s) whichmeet the criteria for a substituted phenyl group (e.g., primary,secondary, tertiary, and quaternary carbon atom groups, among othercriteria) and choose the appropriate substituted phenyl group(s) to meetany particular criteria for a substituted phenyl group(s) for a pyridinebisimine and/or a pyridine bisimine first metal salt described herein.

In an embodiment, each substituted phenyl group which can be utilized asR⁶ and/or R⁷ of the pyridine bisimines and the pyridine bisimine firstmetal salt complexes independently can be a 2-substituted phenyl group,a 3-substituted phenyl group, a 4-substituted phenyl group, a2,3-disubstituted phenyl group, a 2,4-disubstituted phenyl group, a2,5-disubstituted phenyl group, a 3,5-disubstituted phenyl group, a2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group;alternatively, a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, a 2,6-disubstituted phenylgroup, or a 2,4,6-trisubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a4-substituted phenyl group; alternatively, a 2,3-disubstituted phenylgroup; alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,5-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; alternatively, a 2,6-disubstituted phenyl group; oralternatively, a 2,4,6-trisubstituted phenyl group. In some embodiments,each substituted phenyl group which can be utilized as R⁶ and/or R⁷ ofthe pyridine bisimines and the pyridine bisimine first metal saltcomplexes independently can be selected such that (1) one, two, or threeof the 2- and 6-positions of the R⁶ and R⁷ phenyl groups and/orsubstituted phenyl groups independently can be a halogen, a primarycarbon atom group, or a secondary carbon atom group and the remainder ofthe 2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups can be hydrogen, (2) one of the 2- and 6-positions of theR⁶ and R⁷ phenyl groups and/or substituted phenyl groups can be atertiary carbon atom group, none, one, or two of the 2- and 6-positionsof the R⁶ and R⁷ phenyl groups and/or substituted phenyl groupsindependently can be a halogen, a primary carbon atom group or asecondary carbon atom group, and the remainder of the 2- and 6-positionsof the R⁶ and R⁷ phenyl groups and/or substituted phenyl groups can behydrogen, (3) two of the 2- and 6-positions of the R⁶ and R⁷ phenylgroups and/or substituted phenyl groups can be a tertiary carbon atomgroup, none, or one of the 2- and 6-positions of the R⁶ and R⁷ phenylgroups and/or substituted phenyl groups independently can be a halogen,a primary carbon atom group, or a secondary carbon atom group, and theremainder of the 2- and 6-positions of the R⁶ and R⁷ phenyl groupsand/or substituted phenyl groups can be hydrogen, (4) one or two of the2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups can be a tertiary carbon atom group and the remainder ofthe 2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups can be hydrogen, 5) one or two of the 2- and 6-positionsof the R⁶ and R⁷ phenyl groups and/or substituted phenyl groups can be aquaternary carbon atom group and the remainder of the 2- and 6-positionsof the R⁶ and R⁷ phenyl groups and/or substituted phenyl groups can behydrogen, or 6) all four of 2- and 6-positions of the R⁶ and R⁷substituted phenyl groups can be fluorine. Each substituent of asubstituted aryl group (general or specific) or a substituted phenylgroup (general or specific) which can be utilized as R⁶ and/or R⁷ can bea halide, an alkyl group, or a hydrocarboxy group; alternatively, ahalide or an alkyl group; alternatively, a halide or a hydrocarboxygroup; alternatively, an alkyl group or a hydrocarboxy group;alternatively, a halide; alternatively, an alkyl group; oralternatively, a hydrocarboxy group. Halides, alkyl groups (general andspecific), and hydrocarboxy groups (general and specific) that can beutilized as substituents are independently disclosed herein and can beutilized without limitation, and in any combination, to further describeR⁶ and/or R⁷ of the pyridine bisimines and the pyridine bisimine firstmetal salt complexes. Further, one having ordinary skill in the art canrecognize the independently described substituted phenyl group(s) whichmeet the criteria for a substituted phenyl group (e.g., primary,secondary, tertiary, and quaternary carbon atom groups, among othercriteria) and choose the appropriate substituted phenyl group(s) to meetany particular criteria for a substituted phenyl group(s) for a pyridinebisimine and/or a pyridine bisimine first metal salt described herein.

In an embodiment, R⁶ and/or R⁷ of the pyridine bisimines and thepyridine bisimine first metal salt complexes independently can be aphenyl group, a 2-methylphenyl group, a 2-ethylphenyl group, a2-isopropylphenyl group, a 2-tert-butylphenyl group, a 2-(phenyl)phenylgroup, a 2-trifluoromethylphenyl group, a 2-fluorophenyl group, a2-methoxyphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group, a4-isopropylphenyl group, a 4-tert-butylphenyl group, a 4-fluorophenylgroup, a 4-trifluoromethylphenyl group, a 4-methoxyphenyl group, a2,3-dimethyl phenyl group, a 2-fluoro-3-methylphenyl group, a2,4-dimethylphenyl group, a 2,4-diethylphenyl group, a2,4-diisopropylphenyl group, a 2,4-di-tert-butylphenyl group, a2-fluoro-4-methylphenyl group, a 2,5-dimethylphenyl group, a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-diisopropylphenyl group, a 2,6-diphenylphenyl group, a2-fluoro-6-methylphenyl group, a 2,6-bis(trifluoromethyl)phenyl group, a2,6-difluorophenyl group, a 3,5-dimethylphenyl group, a3,5-diethylphenyl group, a 3,5-diisopropylphenyl group, a3,5-di-tert-butylphenyl group, a 3,5-di(trifluoromethyl)phenyl group, ora 2,4,6-trimethylphenyl group. In some embodiments, R⁶ and/or R⁷ of thepyridine bisimines and the pyridine bisimine first metal salt complexesindependently can be selected such that (1) one, two, or three of the 2-and 6-positions of the R⁶ and R⁷ phenyl groups and/or substituted phenylgroups independently can be a halogen, a primary carbon atom group, or asecondary carbon atom group and the remainder of the 2- and 6-positionsof the R⁶ and R⁷ phenyl groups and/or substituted phenyl groups can behydrogen, (2) one of the 2- and 6-positions of the R⁶ and R⁷ phenylgroups and/or substituted phenyl groups can be a tertiary carbon atomgroup, none, one, or two of the 2- and 6-positions of the R⁶ and R⁷phenyl groups and/or substituted phenyl groups independently can be ahalogen, a primary carbon atom group or a secondary carbon atom group,and the remainder of the 2- and 6-positions of the R⁶ and R⁷ phenylgroups and/or substituted phenyl groups can be hydrogen, (3) two of the2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups can be a tertiary carbon atom group, none, or one of the2- and 6-positions of the R⁶ and R⁷ phenyl groups and/or substitutedphenyl groups independently can be a halogen, a primary carbon atomgroup, or a secondary carbon atom group, and the remainder of the 2- and6-positions of the R⁶ and R⁷ phenyl groups and/or substituted phenylgroups can be hydrogen, (4) one or two of the 2- and 6-positions of theR⁶ and R⁷ phenyl groups and/or substituted phenyl groups can be atertiary carbon atom group and the remainder of the 2- and 6-positionsof the R⁶ and R⁷ phenyl groups and/or substituted phenyl groups can behydrogen, 5) one or two of the 2- and 6-positions of the R⁶ and R⁷phenyl groups and/or substituted phenyl groups can be a quaternarycarbon atom group and the remainder of the 2- and 6-positions of the R⁶and R⁷ phenyl groups and/or substituted phenyl groups can be hydrogen,or 6) all four of the 2- and 6-positions of the R⁶ and R⁷ substitutedphenyl groups can be fluorine. One having ordinary skill in the art canrecognize the independently described substituted phenyl group(s) whichmeet the criteria for a substituted phenyl group (e.g., primary,secondary, and tertiary carbon atom groups, among other criteria) andchoose the appropriate substituted phenyl group(s) to meet anyparticular criteria for a substituted phenyl group(s) for a pyridinebisimine and/or a pyridine bisimine first metal salt described herein.

In an embodiment, the pyridine bisimine or the pyridine bisimine of thepyridine bisimine first metal salt complex can comprise, consistessentially of, or can be, a 2,6-bis[(aryl-imine)hydrocarbyl]pyridine, abis[(substituted arylimine)hydrocarbyl]pyridine, or an[(arylimine)-hydrocarbyl], [(substituted arylimine)hydrocarbyl]pyridine;alternatively, a 2,6-bis[(arylimine)hydrocarbyl]pyridine; alternatively,a bis[(substituted arylimine)hydrocarbyl]pyridine; or alternatively, an[(arylimine)hydrocarbyl], or a [(substitutedarylimine)hydrocarbyl]pyridine. In an aspect, the pyridine bisiminefirst metal salt complex can comprise, can consist essentially of, orcan be, a 2,6-bis[(arylimine)hydrocarbyl]pyridine first metal saltcomplex, a bis[(substituted arylimine)hydrocarbyl]pyridine first metalsalt complex, or an [(arylimine)hydrocarbyl],[(substitutedarylimine)-hydrocarbyl]pyridine first metal salt complex; alternatively,a 2,6-bis[(arylimine)hydrocarbyl]pyridine first metal salt complex;alternatively, a bis[(substituted arylimine)hydrocarbyl]pyridine firstmetal salt complex; or alternatively, an[(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridinefirst metal salt complex. In some aspects, the aryl groups of the2,6-bis[(arylimine)hydrocarbyl]pyridine or the2,6-bis[(arylimine)hydrocarbyl]pyridine first metal salt complex can bethe same or can be different; alternatively, the same; or alternatively,different. In some aspects, the substituted aryl groups of the2,6-bis[(substituted arylimine)hydrocarbyl]pyridine or the2,6-bis[(substituted arylimine)hydrocarbyl]pyridine first metal saltcomplex can be the same or can be different; alternatively, the same; oralternatively, different. In an aspect, the pyridine bisimine or thepyridine bisimine of the pyridine bisimine first metal salt complex cancomprise, consist essentially of, or can be, a2,6-bis[(arylimine)hydrocarbyl]pyridine, a bis[(substitutedarylimine)hydrocarbyl]pyridine, and/or an[(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridinewherein 1) one, two, or three of the aryl groups and/or substituted arylgroups positioned ortho to the carbon atom attached to the iminenitrogen independently can be a halogen, a primary carbon atom group, ora secondary carbon atom group and the remainder of the aryl groupsand/or substituted aryl groups positioned ortho to the carbon atomattached to the imine nitrogen can be hydrogen, 2) one of the arylgroups and/or substituted aryl groups positioned ortho to the carbonatom attached to the imine nitrogen can be a tertiary carbon atom group,none, one, or two of the aryl groups and/or substituted aryl groupspositioned ortho to the carbon atom attached to the imine nitrogenindependently can be a halogen, a primary carbon atom group or asecondary carbon atom group, and the remainder of the aryl groups and/orsubstituted aryl groups positioned ortho to the carbon atom attached tothe imine nitrogen can be hydrogen, 3) two of the aryl groups and/orsubstituted aryl groups positioned ortho to the carbon atom attached tothe imine nitrogen independently can be a tertiary carbon atom group,none, or one of the aryl groups and/or substituted aryl groupspositioned ortho to the carbon atom attached to the imine nitrogenindependently can be a halogen, a primary carbon atom group, or asecondary carbon atom group, and the remainder of the aryl groups and/orsubstituted aryl groups positioned ortho to the carbon atom attached tothe imine nitrogen can be hydrogen, 4) one or two of the aryl groupsand/or substituted aryl groups positioned ortho to the carbon atomattached to the imine nitrogen independently can be a tertiary carbonatom group(s) and the remainder of the aryl groups and/or substitutedaryl groups positioned ortho to the carbon atom attached to the iminenitrogen can be hydrogen, 5) one or two of the aryl groups and/orsubstituted aryl groups positioned ortho to the carbon atom attached tothe imine nitrogen can be a quaternary carbon atom group and theremainder of the aryl groups and/or substituted aryl groups positionedortho to the carbon atom attached to the imine nitrogen can be hydrogen,or 6) all four of the substituted aryl groups positioned ortho to thecarbon atom attached to the imine nitrogen can be fluorine. Hydrocarbylgroups (general and specific), aryl groups (general and specific), andsubstituted aryl groups (general and specific) are independentlydescribed herein. The independent descriptions of the hydrocarbyl group,aryl groups, and substituted aryl groups can be utilized withoutlimitation, and in any combination, to further describe the2,6-bis[(arylimine)hydrocarbyl]pyridine, the bis[(substitutedarylimine)hydrocarbyl]pyridine, or the[(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridinewhich can be utilized as the pyridine bisimine or the pyridine bisiminefirst metal salt complex that can be utilized in the processes describedherein. One having ordinary skill in the art can recognize theindependently described aryl group(s) and/or substituted aryl group(s)which meet the criteria for aryl group and/or substituted aryl groups(e.g., primary, secondary, and tertiary carbon atom groups, among othercriteria) and choose the appropriate aryl group(s) and/or substitutedaryl group(s) to meet any particular criteria for the aryl group(s)and/or substituted phenyl group(s) for a pyridine bisimine and/or apyridine bisimine first metal salt complex described herein.

In an embodiment, the pyridine bisimine and/or the pyridine bisimine ofthe pyridine bisimine first metal salt complex can be2,6-bis[(phenylimine)methyl]pyridine,2,6-bis[(2-methylphenyl-imine)methyl]pyridine,2,6-bis[(2-ethylphenylimine)methyl]pyridine,2,6-bis[(2-isopropylphenylimine)-methyl]pyridine,2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine,2,6-bis[(2,6-diethylphenylimine)-methyl]pyridine,2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)methyl]pyridine,2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridine,or2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridine.

Additional descriptions of pyridine bisimines and pyridine bisiminefirst metal salt complexes suitable for use in the present disclosurecan be found in U.S. Pat. Nos. 5,955,555, 6,103,946, 6,291,733,6,489,497, 6,451,939, 6,455,660, 6,458,739, 6,472,341, 6,545,108,6,559,091, 6,657,026, 6,683,187, 6,710,006, 6,911,505, 6,911,506,7,001,964, 7,045,632, 7,056,997, 7,223,893, 7,456,284, 7,683,149,7,902,415, 7,994,376 and EP 1229020A1.

In various aspects and embodiments, a phenanthroline imine (which alsocan be referred to as a 1,10-phenanthroline-2-imine or a2-iminyl-1,10-phenanthroline) and a metal salt, or a phenanthrolineimine first metal salt complex (which also can be referred to as a1,10-phenanthroline-2-imine first metal salt complex or a2-iminyl-1,10-phenanthroline first metal salt complex) can be utilizedin the processes described herein. Generally, the phenanthroline imine,or the phenanthroline imine of the phenanthroline imine first metal saltcomplex, can be any phenanthroline imine, or any phenanthroline imine ofthe phenanthroline imine first metal salt complex, that when contactedwith the other materials of the process described herein (e.g., metalsalt, ethylene, organoaluminum compound and/or any other appropriatereagent(s)), under the appropriate conditions, can form an oligomerproduct. Generally, the phenanthroline imine and the metal salt, or thephenanthroline imine first metal salt complex (or the phenanthrolineimine and the first metal salt of the phenanthroline imine first metalsalt complex) are independent elements of the processes described hereinand are independently disclosed herein. The independent descriptions ofthe phenanthroline imine and the metal salt, or the phenanthroline iminefirst metal salt complex (or the phenanthroline imine and the firstmetal salt of the phenanthroline imine first metal salt complex) can beused without limitation, and in any combination, to further describe theprocesses that can be utilized in the aspects and/or embodiments of theprocesses described herein.

In an aspect, the phenanthroline imine can have Structure PTI I. In anaspect, the phenanthroline imine first metal salt complex can haveStructure PTIMC I.

R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ of the phenanthrolineimine having Structure PTI I or phenanthroline imine first metal saltcomplex having Structure PTIMC I are independent elements of thephenanthroline imine having Structure PTI I and the phenanthroline iminefirst metal salt complex having Structure PBIMC I and are independentlydescribed herein. The independent descriptions of R¹¹, R¹², R¹³, R¹⁴,R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ can be utilized without limitation, and inany combination, to further describe the phenanthroline imine havingStructure PTI I and/or the phenanthroline imine first metal salt complexhaving Structure PBIMC I. Additionally, the first metal salt, MX_(n), isindependently described herein and can be combined, without limitation,with the independently described R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸,and R¹⁹ to further describe the phenanthroline imine first metal saltcomplex structures described herein.

Generally, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ of the phenanthrolineimines and phenanthroline imine first metal salt complexes,independently can be hydrogen, an inert functional group, or an organylgroup; alternatively, hydrogen or an organyl group; alternatively, aninert functional group or an organyl group; alternatively, hydrogen, aninert functional group, or an organyl group consisting essentially ofinert functional groups; alternatively, hydrogen or an organyl groupconsisting essentially of inert functional groups; alternatively, aninert functional group or an organyl group consisting essentially ofinert functional groups; alternatively, hydrogen, an inert functionalgroup, or a hydrocarbyl group; alternatively, hydrogen or a hydrocarbylgroup; alternatively, an inert functional group or a hydrocarbyl group;alternatively, hydrogen or an inert functional group; alternatively,hydrogen; alternatively, an inert functional group; alternatively, anorganyl group; alternatively, organyl group consisting essentially ofinert functional groups; or alternatively, a hydrocarbyl group. In anyaspect and/or embodiment disclosed herein, the organyl groups which canbe utilized as R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and/or R¹⁹, independentlycan be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organylgroup. In any aspect and/or embodiment disclosed herein, the organylgroups consisting essentially of inert functional groups which can beutilized as R¹³, R¹⁴, R¹⁵, R¹⁶, R¹, R¹⁸, and/or R¹⁹ independently can bea C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl groupconsisting essentially of inert functional groups. In any aspect and/orembodiment disclosed herein, the hydrocarbyl groups which can beutilized as R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ independently can be aC₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ hydrocarbyl group. Insome embodiments, the inert functional groups which can be utilized asR¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ independently can be a halide oran alkoxy group; alternatively, a halide; or alternatively, an alkoxygroup.

In any aspect and/or embodiment disclosed herein, the hydrocarbyl groupwhich can be utilized as R¹¹, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and/or R¹⁹ of thephenanthroline imines and phenanthroline imine first metal saltcomplexes which have an R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and/or R¹⁹ group,independently can be a C₁ to C₂₀, a C₁ to C₁₀, or a C₁ to C₅. In anaspect, the alkyl groups which can be utilized as R¹³, R¹⁴, R¹⁵, R¹⁶,R¹⁷, R¹⁸, and/or R¹⁹ of the phenanthroline imines and phenanthrolineimine first metal salt complexes which have an R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, and/or R¹⁹ group, independently can be a methyl group, an ethylgroup, a propyl group, a butyl group, a pentyl group, a hexyl group, aheptyl group, or an octyl group. In some aspects, the R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, R¹⁸, and/or R¹⁹ alkyl groups of the phenanthroline imines andphenanthroline imine first metal salt complexes which have an R¹³, R¹⁴,R¹⁵, R¹⁶, R¹⁷, R¹⁸, and/or R¹⁹ alkyl group, independently can be amethyl group, an ethyl group, an iso-propyl (2-propyl) group, atert-butyl (2-methyl-2-propyl) group, or a neopentyl(2,2-dimethyl-1-propyl) group; alternatively, a methyl group;alternatively, an ethyl group; alternatively, a n-propyl (1-propyl)group; alternatively, an iso-propyl (2-propyl) group; alternatively, atert-butyl (2-methyl-2-propyl) group; or alternatively, a neopentyl(2,2-dimethyl-1-propyl) group.

In some embodiments, each halide which can be utilized as R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, R¹⁸, and/or R¹⁹ of the phenanthroline imines andphenanthroline imine first metal salt complexes independently can befluoride, chloride, bromide or iodide; alternatively, fluoride,chloride, or bromide; alternatively, fluoride; alternatively, chloride;or alternatively, bromide. In some embodiments, each alkoxy group whichcan be utilized as R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and/or R¹⁹ of thephenanthroline imines and phenanthroline imine first metal saltcomplexes independently can be a C₁ to C₁₀ alkoxy group or a C₁ to C₅alkoxy group. In some embodiments, each alkoxy group which can beutilized as R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ independently can be amethoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group,an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxygroup, an n-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a2-methyl-1-butoxy group, a tert-pentoxy group, a 3-methyl-1-butoxygroup, a 3-methyl-2-butoxy group, or a neo-pentoxy group; alternatively,a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxygroup, or a neo-pentoxy group; alternatively, a methoxy group;alternatively, an ethoxy group; alternatively, an isopropoxy group;alternatively, a tert-butoxy group; or alternatively, a neo-pentoxygroup.

In a particular aspect, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ of thephenanthroline imine each can be hydrogen. In these aspects, thephenanthroline imine can have Structure PTI II. Similarly, in aparticular aspect, R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, and R¹⁹ of thephenanthroline imine first metal salt complex each can be hydrogen. Inthese aspects, the phenanthroline imine first metal salt complex canhave Structure PTIMC II.

R¹¹ and R¹² of the phenanthroline imine having Structure PTI I orStructure PTI II or the phenanthroline imine first metal salt complexhaving Structure PTIMC I or Structure PTIMC II are independent elementsof the phenanthroline imine having Structure PTI I or Structure PTI IIand the phenanthroline imine first metal salt complex having StructurePTIMC I or Structure PTIMC II and are independently described herein.The independent descriptions of R¹¹ and R¹² can be utilized withoutlimitation, and in any combination, to further describe thephenanthroline imine having Structure PTI I or Structure PTI II and/orthe phenanthroline imine first metal salt complex having Structure PTIMCI or Structure PTIMC II. Additionally, the metal salt, MX_(n), isindependently described herein can be combined, without limitation, withthe independently described R¹¹ and R¹² to further describe thephenanthroline imine first metal salt complex having Structure PTIMC Ior Structure PTIMC II.

Generally, R¹¹ of the phenanthroline imines and the phenanthroline iminefirst metal salt complexes can be an aryl group, a substituted arylgroup, a phenyl group, or a substituted phenyl group; alternatively, anaryl group or a substituted aryl group; alternatively, a phenyl group ora substituted phenyl group; alternatively, an aryl group; alternatively,a substituted aryl group; alternatively, a phenyl group; oralternatively, a substituted phenyl group. In any aspect and/orembodiment disclosed herein, the R¹¹ aryl group of the phenanthrolineimines and the phenanthroline imine first metal salt complexes can be aC₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ aryl group. In any aspect and/orembodiment disclosed herein, the R¹¹ substituted aryl groups of thephenanthroline imines and the phenanthroline imine first metal saltcomplexes can be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ substitutedaryl group. In any aspect and/or embodiment disclosed herein, the R¹¹substituted phenyl groups of the phenanthroline imines and thephenanthroline imine first metal salt complexes can be a C₆ to C₂₀, a C₆to C₁₅, or a C₆ to C₁₅ substituted phenyl group. Each substituent of asubstituted aryl group (general or specific) or a substituted phenylgroup (general or specific) which can be utilized as R¹¹ can be ahalide, an alkyl group, or a hydrocarboxy group; alternatively, a halideor an alkyl group; alternatively, a halide or a hydrocarboxy group;alternatively, an alkyl group or a hydrocarboxy group; alternatively, ahalide; alternatively, an alkyl group; or alternatively, a hydrocarboxygroup. Halides, alkyl groups (general and specific), and hydrocarboxygroups (general and specific) that can be utilized as substituents areindependently disclosed herein and can be utilized without limitation,and in any combination, to further describe R¹¹ of the phenanthrolineimines and the phenanthroline imine first metal salt complexes.

In an embodiment, each substituted phenyl group which can be utilized asR¹¹ substituted phenyl groups of the phenanthroline imines and thephenanthroline imine first metal salt complexes can be a substitutedphenyl group comprising a substituent at the 2-position, a substitutedphenyl group comprising a substituent at the 3-position, a substitutedphenyl group comprising a substituent at the 4-position, a disubstitutedphenyl group comprising substituents at the 2- and 3-positions, adisubstituted phenyl group comprising substituents at the 2- and4-positions, a disubstituted phenyl group comprising substituents at the2- and 5-positions, a disubstituted phenyl group comprising substituentsat the 3- and 5-positions, a disubstituted phenyl group comprisingsubstituents at the 2- and 6-positions, or a trisubstituted phenyl groupcomprising substituents at the 2-, 4-, and 6-positions; alternatively, asubstituted phenyl group comprising a substituent at the 2-position, asubstituted phenyl group comprising a substituent at the 4-position, adisubstituted phenyl group comprising substituents at the 2- and4-positions, a disubstituted phenyl group comprising substituents at the2- and 6-positions, or a trisubstituted phenyl group comprisingsubstituents at the 2-, 4-, and 6-position; alternatively, adisubstituted phenyl group comprising substituents at the 2- and6-positions or a trisubstituted phenyl group comprising substituents atthe 2-, 4-, and 6-positions; alternatively, a substituted phenyl groupcomprising a substituent at the 2-position; alternatively, a substitutedphenyl group comprising a substituent at the 3-position; alternatively,a substituted phenyl group comprising a substituent at the 4-position;alternatively, a disubstituted phenyl group comprising substituents atthe 2- and 3-positions; alternatively, a disubstituted phenyl groupcomprising substituents at the 2- and 4-positions; alternatively, adisubstituted phenyl group comprising substituents at the 2- and5-positions; alternatively, a disubstituted phenyl group comprisingsubstituents at the 3- and 5-positions; alternatively, a disubstitutedphenyl group comprising substituents at the 2- and 6-position; oralternatively, a trisubstituted phenyl group comprising substituents atthe 2-, 4-, and 6-positions. In an aspect, each substituted phenyl groupwhich can be utilized as R¹¹ substituted phenyl groups of thephenanthroline imines and the phenanthroline imine first metal saltcomplexes can be a 2-substituted phenyl group, a 3-substituted phenylgroup, a 4-substituted phenyl group, a 2,3-disubstituted phenyl group, a2,4-disubstituted phenyl group, a 2,5-disubstituted phenyl group, a3,5-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2-substituted phenylgroup, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group;alternatively, a 2,6-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2-substituted phenylgroup; alternatively, a 4-substituted phenyl group; alternatively, a2,3-disubstituted phenyl group; alternatively, a 2,4-disubstitutedphenyl group; alternatively, a 2,5-disubstituted phenyl group;alternatively, a 3,5-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; or alternatively, a 2,4,6-trisubstitutedphenyl group. In an aspect where the substituted phenyl group has morethan one substituent, two or more of the substituents can be different,each substituent can be different, or each substituent can be the same;alternatively, two or more of the substituents can be different;alternatively, each substituent can be different; or alternatively, eachsubstituent can be the same. Each substituent of a substituted phenylgroup (general or specific) which can be utilized as R¹¹ independentlycan be a halide, an alkyl group, or a hydrocarboxy group; alternatively,a halide or an alkyl group; alternatively, a halide or a hydrocarboxygroup; alternatively, an alkyl group or a hydrocarboxy group;alternatively, a halide; alternatively, an alkyl group; oralternatively, a hydrocarboxy group. Halides, alkyl groups (general andspecific), and hydrocarboxy groups (general and specific) that can beutilized as substituents are independently disclosed herein and can beutilized without limitation, and in any combination, to further describeR¹¹ of the phenanthroline imines and the phenanthroline imine firstmetal salt complexes.

In an embodiment, each substituted phenyl group which can be utilized asan R¹¹ substituted phenyl group of the phenanthroline imines and thephenanthroline imine first metal salt complexes can be a substitutedphenyl group comprising an alkyl group at the 2-position, a substitutedphenyl group comprising an alkyl group at the 4-position, adisubstituted phenyl group comprising alkyl groups at the 2- and4-positions, a disubstituted phenyl group comprising alkyl groups at the2- and 6-positions, a trisubstituted phenyl group comprising alkylgroups at the 2-, 4-, and 6-positions, a substituted phenyl groupcomprising a halide at the 2-position, a disubstituted phenyl groupcomprising halides at the 2- and 4-positions, or a trisubstituted phenylgroup comprising halides at the 2-, 4-, and 6-positions; alternatively,a substituted phenyl group comprising an alkyl group at the 2-position,a substituted phenyl group comprising an alkyl group at the 4-position,a disubstituted phenyl group comprising alkyl groups at the 2- and4-positions, a disubstituted phenyl group comprising alkyl groups at the2- and 6-positions, or a trisubstituted phenyl group comprising alkylgroups at the 2-, 4-, and 6-positions; alternatively, a substitutedphenyl group comprising a halide at the 2-position, a disubstitutedphenyl group comprising halides at the 2- and 4-positions, or atrisubstituted phenyl group comprising halides at the 2-, 4-, and6-positions; alternatively, a disubstituted phenyl group comprisingalkyl groups at the 2- and 4-positions, or a trisubstituted phenyl groupcomprising alkyl groups at the 2-, 4-, and 6-positions; alternatively, adisubstituted phenyl group comprising alkyl groups at the 2- and4-positions; alternatively, a trisubstituted phenyl group comprisingalkyl groups at the 2-, 4-, and 6-positions; alternatively, substitutedphenyl group comprising a halide at the 2-position; alternatively, adisubstituted phenyl group comprising halides at the 2- and 4-positions;or alternatively, or a trisubstituted phenyl group comprising halides atthe 2-, 4-, and 6-positions. In some embodiments, each substitutedphenyl group which can be utilized as an R¹¹ substituted phenyl group ofthe phenanthroline imines and the phenanthroline imine first metal saltcomplexes can be a 2-alkylphenyl group, a 4-alkylphenyl group, a2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, a2,4,6-trialkylphenyl group, a 2-halophenyl group, a 2,4-dihalophenylgroup, a 2,4,6-trihalophenyl group, a 2,6-dialkyl-4-halophenyl group, ora 2,6-dihalo-4-alkylphenyl group; alternatively, a 2-alkylphenyl group,a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group; alternatively, a2,6-dialkylphenyl group or a 2,4,6-trialkylphenyl group; alternatively,a 2-halophenyl group, a 2,4-dihalophenyl group, or a 2,4,6-trihalophenylgroup; alternatively, a 2,6-dialkyl-4-halophenyl group or a2,6-dihalo-4-alkylphenyl group; alternatively, a 2,6-dialkylphenyl groupor a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group;alternatively, a 4-alkylphenyl group; alternatively, a 2,4-dialkylphenylgroup; alternatively, a 2,6-dialkylphenyl group; alternatively, a2,4,6-trialkylphenyl group; alternatively, a 2-halophenyl group;alternatively, a 2,4-dihalophenyl group; alternatively, a2,4,6-trihalophenyl group; alternatively, a 2,6-dialkyl-4-halophenylgroup; or alternatively, a 2,6-dihalo-4-alkylphenyl group. In anembodiment where the substituted phenyl group has more than onesubstituent, two or more of the substituents can be different, eachsubstituent can be different, or each substituent can be the same;alternatively, two or more of the substituents can be different;alternatively, each substituent can be different; or alternatively, eachsubstituent can be the same. Halides and alkyl groups (general andspecific) that can be utilized as substituents are independentlydisclosed herein and can be utilized without limitation, and in anycombination, to further describe R¹¹ of the phenanthroline imines andthe phenanthroline imine first metal salt complexes.

In an embodiment, the substituted phenyl R¹¹ group of the phenanthrolineimines and the phenanthroline imine first metal salt complexes can be a2-methylphenyl group, a 2-ethylphenyl group, a 2-isopropylphenyl group,a 2-tert-butylphenyl group, a 2-fluorophenyl group, a 2-chlorophenylgroup, a 2-bromophenyl group, a 2,6-dimethylphenyl group, a2,6-diethylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 2,4,6-trimethylphenyl group, a2,6-difluorophenyl group, a 2,6-dichlorophenyl group, a2,6-dibromophenyl group, a 2,4,6-trifluorophenyl group, a2,4,6-trichlorophenyl group, a 2,4,6-tribromophenyl group, a2,4-dibromo-6-chlorophenyl group, a 2,6-dimethyl-6-bromophenyl group, ora 2,6-dibromo-4-methylphenyl group; alternatively, a 2,6-dimethylphenylgroup, a 2,6-diethylphenyl group, a 2,6-diisopropylphenyl group, or a2,4,6-trimethylphenyl group; alternatively, a 2,6-difluorophenyl group,a 2,6-dichlorophenyl group, a 2,6-dibromophenyl group, a2,4,6-tribromophenyl group, or a 2,4-dibromo-6-chlorophenyl group;alternatively, a 2,6-dimethyl-6-bromophenyl group or a2,6-dibromo-6-methylphenyl group; alternatively, a2,6-dimethyl-6-bromophenyl group or a 2,6-dibromo-4-methylphenyl group;alternatively, a 2,6-dimethylphenyl group; alternatively, a2,6-diethylphenyl group; alternatively, a 2,6-diisopropylphenyl group;alternatively, a 2,4,6-trimethylphenyl group; alternatively, a2,6-difluorophenyl group; alternatively, a 2,6-dichlorophenyl group;alternatively, a 2,6-dibromophenyl group; alternatively, a2,4,6-tribromophenyl group; alternatively, a 2,4-dibromo-6-chlorophenylgroup; alternatively, a 2,6-dimethyl-6-bromophenyl group; oralternatively, a 2,6-dibromo-6-methylphenyl group.

Generally, R¹² of the phenanthroline imines and the phenanthroline iminefirst metal salt complexes can be hydrogen or an organyl group;alternatively, hydrogen or an organyl group consisting essentially ofinert functional groups; alternatively, hydrogen or a hydrocarbyl group;alternatively, hydrogen; alternatively, an organyl group; alternatively,an organyl group consisting essentially of inert functional groups; oralternatively, a hydrocarbyl group. In any aspect and/or embodimentdisclosed herein, the R¹² organyl groups of the phenanthroline iminesand the phenanthroline imine first metal salt complexes can be a C₁ toC₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl group. In anyaspect and/or embodiment disclosed herein, the R¹² organyl groupsconsisting essentially of inert functional groups, of the phenanthrolineimines and the phenanthroline imine first metal salt complexes can be aC₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl groupconsisting essentially of inert functional groups. In any aspect and/orembodiment disclosed herein, the R¹² hydrocarbyl groups of thephenanthroline imines and the phenanthroline imine first metal saltcomplexes can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅hydrocarbyl group.

In any aspect and/or embodiment disclosed herein, the R¹² hydrocarbylgroup of any phenanthroline imine and any phenanthroline imine firstmetal salt complex described herein can be an alkyl group, a cycloalkylgroup, a substituted cycloalkyl group, an aryl group, a substituted arylgroup, an aralkyl group, or a substituted aralkyl group. In someembodiments, the R¹² hydrocarbyl group of any phenanthroline imine andany phenanthroline imine first metal salt complex described herein canbe an alkyl group; alternatively, a cycloalkyl group or a substitutedcycloalkyl group; alternatively, an aryl group or a substituted arylgroup; alternatively, an aralkyl group or a substituted aralkyl group;or alternatively, an alkyl group, a cycloalkyl group, an aryl group, oran aralkyl group. In other embodiments, the R¹² hydrocarbyl group of anyphenanthroline imine and any phenanthroline imine first metal saltcomplex described herein can be an alkyl group; alternatively, acycloalkyl group; alternatively, a substituted cycloalkyl group;alternatively, an aryl group; alternatively, a substituted aryl group;alternatively, an aralkyl group; or alternatively, a substituted aralkylgroup. In any aspect or embodiment disclosed herein, each alkyl groupwhich can be utilized as R¹² of the phenanthroline imines and thephenanthroline imine first metal salt complexes can be a C₁ to C₂₀, a C₁to C₁₀, or a C₁ to C₅ alkyl group. In any aspect or embodiment disclosedherein, each cycloalkyl group which can be utilized as R¹² of thephenanthroline imines and the phenanthroline imine first metal saltcomplexes can be a C₄ to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀ cycloalkylgroup. In any aspect or embodiment disclosed herein, each substitutedcycloalkyl group which can be utilized as R¹² can be a C₄ to C₂₀, a C₄to C₁₅, or a C₄ to C₁₀ substituted cycloalkyl group. In any aspect orembodiment disclosed herein, each aryl group which can be utilized asR¹² of the phenanthroline imines and the phenanthroline imine firstmetal salt complexes can be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀aryl group. In any aspect or embodiment disclosed herein, eachsubstituted aryl group which can be utilized as R¹² can be a C₆ to C₂₀,a C₆ to C₁₅, or a C₆ to C₁₀ substituted aryl group. In any aspect orembodiment disclosed herein, each aralkyl group which can be utilizedR¹² of the phenanthroline imines and the phenanthroline imine firstmetal salt complexes can be a C₇ to C₂₀, a C₇ to C₁₅, or a C₇ to C₁₀aralkyl group. In any aspect or embodiment disclosed herein, eachsubstituted aralkyl group which can be utilized as R¹² of thephenanthroline imines and the phenanthroline imine first metal saltcomplexes can be a C₇ to C₂₀, a C₇ to C₁₅, or a C₇ to C₁₀ substitutedaralkyl group. Each substituent of a substituted alkyl group (general orspecific), a substituted cycloalkyl group (general or specific), asubstituted aryl group (general or specific), and/or a substitutedaralkyl group (general or specific) can be a hydrocarbyl group.Substituent hydrocarbyl groups (general and specific) are independentlydisclosed herein. These substituent hydrocarbyl groups can be utilizedwithout limitation to further describe the substituted cycloalkylgroups, the substituted aryl groups, or the substituted aralkyl groupswhich can be utilized as R¹² of the phenanthroline imines and thephenanthroline imine first metal salt complexes.

In any aspect or embodiment disclosed herein, R¹² of any phenanthrolineimine and any phenanthroline imine first metal salt complex describedherein can be hydrogen, a methyl group, an ethyl group, an n-propyl(1-propyl) group, an iso-propyl (2-propyl) group, a tert-butyl(2-methyl-2-propyl) group, a neopentyl (2,2-dimethyl-1-propyl) group, ora phenyl group; alternatively, hydrogen, a methyl group, an ethyl group,an n-propyl (1-propyl) group, an iso-propyl (2-propyl) group, or aphenyl group; alternatively, a methyl group, an ethyl group, an n-propyl(1-propyl) group, or an iso-propyl (2-propyl) group; alternatively,hydrogen; alternatively, a methyl group; alternatively, an ethyl group;alternatively, an n-propyl (1-propyl) group; alternatively, aniso-propyl (2-propyl) group; alternatively, a tert-butyl(2-methyl-2-propyl) group; alternatively, a neopentyl(2,2-dimethyl-1-propyl) group; or alternatively, a phenyl group.

In an embodiment, the phenanthroline imine or the phenanthroline imineof the phenanthroline imine first metal salt complex can comprise, canconsist essentially of, or can be, a2-(hydrocarbylimine)-1,10-phenanthroline, a2-[(hydrocarbylimine)hydrocarbyl]-1,10-phenanthroline, a2-(arylimine)-1,10-phenanthroline, a2-[(arylimine)hydrocarbyl]-1,10-phenanthroline, a 2-(substitutedarylimine)-1,10-phenanthroline, or a 2-[(substitutedarylimine)hydrocarbyl]-1,10-phenanthroline; alternatively, a2-(hydrocarbylimine)-1,10-phenanthroline; alternatively, a2-[(hydrocarbylimine)hydrocarbyl]-1,10-phenanthroline; alternatively, a2-(arylimine)-1,10-phenanthroline; alternatively, a2-[(arylimine)hydrocarbyl]-1,10-phenanthroline; alternatively, a2-(substituted arylimine)-1,10-phenanthroline; or alternatively, a2-[(substituted arylimine)hydrocarbyl]-1,10-phenanthroline.

In an embodiment, the phenanthroline imine or the phenanthroline imineof the phenanthroline imine first metal salt complex can comprise, canconsist essentially of, or can be, a 2-(2,6-disubstitutedphenylimine)-1,10-phenanthroline, a 2-[(2,6-disubstitutedphenylimine)alkyl]-1,10-phenanthroline, a 2-[(2,6-disubstitutedphenylimine)phenyl]-1,10-phenanthroline, a 2-(2,4,6-trisubstitutedphenylimine)-1,10-phenanthroline, a 2-[(2,4,6-trisubstitutedphenylimine)alkyl]-1,10-phenanthroline, or a 2-[(2,4,6-trisubstitutedphenylimine)phenyl]-1,10-phenanthroline; alternatively, a2-(2,6-disubstituted phenylimine)-1,10-phenanthroline; alternatively, a2-[(2,6-disubstituted phenylimine)alkyl]-1,10-phenanthroline;alternatively, a 2-[(2,6-disubstitutedphenylimine)phenyl]-1,10-phenanthroline; alternatively, a2-(2,4,6-trisubstituted phenylimine)-1,10-phenanthroline; alternatively,a 2-[(2,4,6-trisubstituted phenylimine)alkyl]-1,10-phenanthroline; oralternatively, a 2-[(2,4,6-trisubstitutedphenylimine)phenyl]-1,10-phenanthroline. Each substituent of a2-(2,6-disubstituted phenylimine)-1,10-phenanthroline, a2-[(2,6-disubstituted phenylimine)alkyl]-1,10-phenanthroline, a2-[(2,6-disubstituted phenylimine)phenyl]-1,10-phenanthroline, a2-(2,4,6-trisubstituted phenylimine)-1,10-phenanthroline, a2-[(2,4,6-trisubstituted phenylimine)alkyl]-1,10-phenanthroline, or a2-[(2,4,6-trisubstituted phenylimine)phenyl]-1,10-phenanthroline can bean alkyl group or a halo group; alternatively, an alkyl group; oralternatively, a halo group. Substituent alkyl groups (general andspecific) and halo group are independently disclosed herein. Thesesubstituent alkyl groups and halo groups can be utilized withoutlimitation to further describe the substituents of the phenanthrolineimines or the phenanthroline imines of the phenanthroline imine firstmetal salt complexes.

In an embodiment, the phenanthroline imine or the phenanthroline imineof the phenanthroline imine first metal salt complex can comprise, canconsist essentially of, or can be, a2-(2,6-dialkylphenylimine)-1,10-phenanthroline, a2-[(2,6-dialkylphenylimine)alkyl]-1,10-phenanthroline, a2-[(2,6-dialkylphenylimine)phenyl]-1,10-phenanthroline, a2-(2,4,6-trialkylphenylimine)-1,10-phenanthroline, a2-[(2,4,6-trialkylphenylimine)alkyl]-1,10-phenanthroline, a2-[(2,4,6-trialkylphenyl-imine)phenyl]-1,10-phenanthroline, a2-(2,6-dihalophenylimine)-1,10-phenanthroline, a2-[(2,6-dihalo-phenylimine)alkyl]-1,10-phenanthroline, a2-[(2,6-dihalophenylimine)phenyl]-1,10-phenanthroline,2-(2,4,6-trihalophenylimine)-1,10-phenanthroline, a2-(2,6-dialkyl-4-halophenylimine)-1,10-phenanthroline, or a2-(2,6-dihalo-4-alkyl-phenylimine)-1,10-phenanthroline; alternatively, a2-(2,6-dialkylphenylimine)-1,10-phenanthroline; alternatively, a2-[(2,6-dialkylphenylimine)alkyl]-1,10-phenanthroline; alternatively, a2-[(2,6-dialkylphenylimine)phenyl]-1,10-phenanthroline; alternatively, a2-(2,4,6-trialkylphenylimine)-1,10-phenanthroline; alternatively, a2-[(2,4,6-trialkylphenylimine)alkyl]-1,10-phenanthroline; alternatively,a 2-[(2,4,6-trialkylphenylimine)phenyl]-1,10-phenanthroline;alternatively, a 2-(2,6-dihalophenylimine)-1,10-phenanthroline;alternatively, a 2-[(2,6-dihalo-phenylimine)alkyl]-1,10-phenanthroline;alternatively, a 2-[(2,6-dihalophenylimine)phenyl]-1,10-phenanthroline;alternatively, 2-(2,4,6-trihalophenylimine)-1,10-phenanthroline;alternatively, a 2-(2,6-dialkyl-4-halophenylimine)-1,10-phenanthroline;or alternatively, a2-(2,6-dihalo-4alkyl-phenylimine)-1,10-phenanthroline. Substituent alkylgroups (general and specific) and halo groups are independentlydisclosed herein. These substituent alkyl groups and halo groups can beutilized without limitation to further describe the substituents of thephenanthroline imines or the phenanthroline imines of the phenanthrolineimine first metal salt complexes.

In a non-limiting embodiment, the phenanthroline imine or thephenanthroline imine of the phenanthroline imine first metal saltcomplex can comprise, can consist essentially of, or can be,2-(2,6-difluorophenylimine)-1,10-phenanthroline,2-(2,6-dichlorophenylimine)-1,10-phenanthroline,2-(2,6-dibromophenylimine)-1,10-phenanthroline,2-(2,6-dimethylphenylimine)-1,10-phenanthroline,2-(2,6-diethylphenylimine)-1,10-phenanthroline,2-(2,6-diisopropylphenylimine)-1,10-phenanthroline,2-[(2,6-difluorophenylimine)methyl]-1,10-phenanthroline,2-[(2,6-dichlorophenylimine)methyl]-1,10-phenanthroline,2-[(2,6-dibromophenylimine)methyl]-1,10-phenanthroline,2-[(2,6-dimethylphenylimine)-methyl]-1,10-phenanthroline,2-[(2,6-diethylphenylimine)methyl]-1,10-phenanthroline,2-[(2,6-diisopropylphenylimine)methyl]-1,10-phenanthroline,2-[(2,6-diethylphenylimine)ethyl]-1,10-phenanthroline,2-[(2,6-diethylphenylimine)-n-propyl]-1,10-phenanthroline,2-[(2,6-diethylphenylimine)iso-propyl]-1,10-phenanthroline,2-[(2,4,6-tribromophenylamine)methyl]-1,10-phenanthroline,2-[(2,4,6-trimethylphenyl-imine)methyl]-1,10-phenanthroline,2-[(2,6-dimethyl-4-bromophenylimine)methyl]-1,10-phenanthroline,2-[(2,6-dibromo-4-methylphenylimine)methyl]-1,10-phenanthroline,2-[(2,6-dibromo-4-chlorophenyl-imine)methyl]-1,10-phenanthroline,2-[(2,6-dimethylphenylimine)phenyl]-1,10-phenanthroline,2-[(2,6-diethylphenylimine)phenyl]-1,10-phenanthroline, and2-[(2,6-diisopropylphenylimine)phenyl]-1,10-phenanthroline.

The processes described herein can utilize a metal salt, a first metalsalt (as a part of any heteroatomic ligand metal salt complex comprisinga heteroatomic ligand complexed to a first metal salt disclosed herein),and/or a second metal salt. In any aspect and/or embodiments utilizing ametal salt, a first metal salt (as a part of any heteroatomic ligandmetal salt complex comprising a heteroatomic ligand complexed to a firstmetal salt disclosed herein), and/or a second metal salt, the metalsalt, first metal salt, and second metal salt are independent of eachother and can be the same or different: alternatively, the same; oralternatively different. Generally, the metal salt, the first metal salt(as a part of any heteroatomic ligand metal salt complex comprising aheteroatomic ligand complexed to a first metal salt disclosed herein),and/or the second metal salt, can have the formula MX_(n). Within theformula of the metal salt having the formula MX_(n) (whether it is themetal salt, the first metal salt, and/or a second metal salt), Mrepresents the metal atom, X represents a monoanionic species, and nrepresents the number of monoanionic species (or the metal oxidationstate). Generally, the metal, the monoanionic species, X, and the numberof anionic species (or the metal oxidation state), n, are independentelements of the metal salt (whether it is the metal salt, the firstmetal salt, and/or a second metal salt) and are independently describedherein. The metal salt having the formula MX_(n) (whether it is themetal salt, the first metal salt, and/or the second metal salt) can bedescribed utilizing any aspect and/or embodiment of the metal describedherein, any aspect or embodiment of the monoanionic specie describedherein, and any aspect and/or embodiment of the number of monoanionicspecies (or metal oxidation state) described herein.

Generally, the metal of the metal salt (whether it is the metal salt,the first metal salt, and/or the second metal salt) independently can bea group 8 or group 9 metal; alternatively, a group 8 metal; oralternatively, a group 9 metal. In some embodiments, metal of the metalsalt which can be utilized as the metal salt, the first metal salt (as apart of any heteroatomic ligand metal salt complex comprising aheteroatomic ligand complexed to a first metal salt described herein),and/or the second metal salt independently can be iron (Fe) or cobalt(Co); alternatively, iron (Fe); or alternatively, cobalt (Co).Generally, the oxidation state of the metal of the metal salt and/ornumber, n, of monoanionic species, X, of the metal salt which can beutilized as the metal salt, the first metal salt (as a part of anyheteroatomic ligand metal salt complex comprising a heteroatomic ligandcomplexed to a first metal salt described), and/or the second metal saltindependently can be any positive integer that corresponds to anoxidation state available to the metal atom. In an aspect, the oxidationstate of the metal of the metal salt and/or number, n, of monoanionicspecies, X, of the metal salt which can be utilized as the metal salt,the first metal salt (as a part of any heteroatomic ligand metal saltcomplex comprising a heteroatomic ligand complexed to a first metal saltdescribed herein), and/or the second metal salt independently can be 1,2 or 3; alternatively, 2 or 3; alternatively, 1; alternatively, 2; oralternatively, 3.

Generally, the monoanionic specie, X, of the metal salt, the first metalsalt (as a part of any heteroatomic ligand metal salt complex comprisinga heteroatomic ligand complexed to a first metal salt described herein),and/or the second metal salt independently can be any monoanionicspecie. In an aspect, the monoanionic specie, X, can be a halide, acarboxylate, a β-diketonate, a hydrocarboxide, a nitrate, or a chlorate;alternatively, a halide, a carboxylate, a β-diketonate, or ahydrocarboxide; or alternatively, a halide, a carboxylate, or aβ-diketonate. In any aspect and/or embodiment, the hydrocarboxide can bean alkoxide, an aryloxide, or an aralkoxide. Generally, hydrocarboxides(and subdivisions of hydrocarboxide) are the anion analogues of thehydrocarboxy group. In other aspects, the monoanionic specie, X, of themetal salt, the first metal salt (as a part of any heteroatomic ligandmetal salt complex comprising a heteroatomic ligand complexed to a firstmetal salt described herein), and/or the second metal salt independentlycan be a halide, a carboxylate, a β-diketonate, or an alkoxide;alternatively, a carboxylate; alternatively, a β-diketonate;alternatively, a hydrocarboxide; alternatively, an alkoxide; oralternatively, an aryloxide.

Generally, each halide monoanionic specie, X, of the metal salt, thefirst metal salt (as a part of any heteroatomic ligand metal saltcomplex comprising a heteroatomic ligand complexed to a first metal saltdescribed herein), and/or the second metal salt independently can befluorine, chlorine, bromine, or iodine; or alternatively, chlorine,bromine, or iodine. In an aspect, each halide monoanionic specie, X, ofthe metal salt, the first metal salt (as a part of any heteroatomicligand metal salt complex comprising a heteroatomic ligand complexed toa first metal salt described herein), and/or the second metal saltindependently can be chlorine; alternatively, bromine; or alternatively,iodine.

Generally, each carboxylate monoanionic specie, X, of the metal salt,the first metal salt (as a part of any heteroatomic ligand metal saltcomplex comprising a heteroatomic ligand complexed to a first metal saltdescribed herein), and/or the second metal salt independently can be aC₁ to C₂₀ or a C₁ to C₁₀ carboxylate. In an aspect, each carboxylate ofthe metal salt, the first metal salt (as a part of any heteroatomicligand metal salt complex comprising a heteroatomic ligand complexed toa first metal salt described herein), and/or the second metal saltindependently can be acetate, a propionate, a butyrate, a pentanoate, ahexanoate, a heptanoate, an octanoate, a nonanoate, a decanoate, anundecanoate, or a dodecanoate; or alternatively, a pentanoate, ahexanoate, a heptanoate, an octanoate, a nonanoate, or a decanoate. Insome aspects, each carboxylate monoanionic specie, X, of the metal salt,the first metal salt (as a part of any heteroatomic ligand metal saltcomplex comprising a heteroatomic ligand complexed to a first metal saltdescribed herein), and/or the second metal salt independently can beacetate, propionate, n-butyrate, valerate (n-pentanoate),neo-pentanoate, capronate (n-hexanoate), n-heptanoate, caprylate(n-octanoate), 2-ethylhexanoate, n-nonanoate, caprate (n-decanoate),n-undecanoate, or laurate (n-dodecanoate); alternatively, valerate(n-pentanoate), neo-pentanoate, capronate (n-hexanoate), n-heptanoate,caprylate (n-octanoate), 2-ethylhexanoate, n-nonanoate, or caprate(n-decanoate; alternatively, n-heptanoate; alternatively, caprylate(n-octanoate); or alternatively, 2-ethylhexanoate. In some aspects, thecarboxylate can be triflate (trifluoroacetate).

Generally, each β-diketonate monoanionic specie, X, of the metal salt,the first metal salt (as a part of any heteroatomic ligand metal saltcomplex comprising a heteroatomic ligand complexed to a first metal saltdescribed herein), and/or the second metal salt independently can be aC₁ to C₂₀ or a C₁ to C₁₀ β-diketonate. In an aspect, each β-diketonatemonoanionic specie, X, of the metal salt, the first metal salt (as apart of any heteroatomic ligand metal salt complex comprising aheteroatomic ligand complexed to a first metal salt described herein),and/or the second metal salt independently can be acetylacetonate (i.e.,2,4-pentanedionate), hexafluoroacetylacetonate (i.e.,1,1,1,5,5,5-hexafluoro-2,4-pentanedionate), or benzoylacetonate;alternatively, acetylacetonate; alternatively, hexafluoroacetylacetone;or alternatively, benzoylacetonate.

Generally, each hydrocarboxide monoanionic specie, X, of the metal salt,the first metal salt (as a part of any heteroatomic ligand metal saltcomplex comprising a heteroatomic ligand complexed to a first metal saltdescribed herein), and/or the second metal salt independently can be anyC₁ to C₂₀ or C₁ to C₁₀ hydrocarboxide. In an aspect, each hydrocarboxidemonoanionic specie, X, of the metal salt, the first metal salt (as apart of any heteroatomic ligand metal salt complex comprising aheteroatomic ligand complexed to a first metal salt described herein),and/or the second metal salt independently can be a C₁ to C₂₀ alkoxide;alternatively, a C₁ to C₁₀ alkoxide; alternatively, a C₆ to C₂₀aryloxide; or alternatively, a C₆ to C₁₀ aryloxide. In an aspect, eachalkoxide monoanionic specie, X, of the metal salt, the first metal salt(as a part of any heteroatomic ligand metal salt complex comprising aheteroatomic ligand complexed to a first metal salt described herein),and/or the second metal salt independently can be methoxide, ethoxide, apropoxide, or a butoxide. In some aspects, each alkoxide monoanionicspecie, X, of the metal salt, the first metal salt (as a part of anyheteroatomic ligand metal salt complex comprising a heteroatomic ligandcomplexed to a first metal salt described herein), and/or the secondmetal salt independently can be methoxide, ethoxide, isopropoxide, ortert-butoxide; alternatively, methoxide; alternatively, an ethoxide;alternatively, an iso-propoxide; or alternatively, a tert-butoxide. Inan aspect, each aryloxide monoanionic specie, X, of the metal salt, thefirst metal salt (as a part of any heteroatomic ligand metal saltcomplex comprising a heteroatomic ligand complexed to a first metal saltdescribed herein), and/or the second metal salt independently can bephenoxide.

In any aspect or embodiment, the metal salt, the first metal salt (as apart of any heteroatomic ligand metal salt complex comprising aheteroatomic ligand complexed to a first metal salt described herein),and/or the second metal salt independently can comprise, can consistessentially of, or can be an iron salt, a cobalt salt, or a combinationthereof; alternatively, an iron salt; or alternatively, a cobalt salt.In an embodiment, the metal salt, the first metal salt (as a part of anyheteroatomic ligand metal salt complex comprising a heteroatomic ligandcomplexed to a first metal salt described herein), and/or the secondmetal salt independently can comprise, can consist essentially of, orcan be an iron halide, a cobalt halide, an iron β-diketonate, a cobaltβ-diketonate, an iron carboxylate, a cobalt carboxylate or anycombination thereof; alternatively, an iron halide, an ironβ-diketonate, an iron carboxylate, or any combination thereof; oralternatively, an cobalt halide, an cobalt β-diketonate, an cobaltcarboxylate, or any combination thereof. In any aspect or embodiment,the metal salt, the first metal salt (as a part of any heteroatomicligand metal salt complex comprising a heteroatomic ligand complexed toa first metal salt described herein), and/or the second metal saltindependently can comprise, can consist essentially of, or can be,iron(II) fluoride, cobalt(II) fluoride, iron(III) fluoride, cobalt(III)fluoride, iron(II) bromide, cobalt(II) bromide, iron(III) bromide,cobalt(III) bromide, iron(II) iodide, cobalt(II) iodide, iron(III)iodide, cobalt(III) iodide, iron(II) acetate, cobalt(II) acetate,iron(III) acetate, iron(III) acetate, iron(II) acetylacetonate,cobalt(II) acetylacetonate, iron(III) acetylacetonate, cobalt(III)acetylacetonate, iron(II) 2-ethylhexanoate, cobalt(II) 2-ethylhexanoate,iron(III) 2-ethylhexanoate, cobalt(III) 2-ethylhexanoate, iron(II)triflate, cobalt(II) triflate, iron(III) triflate, cobalt(III) triflate,iron(II) nitrate, cobalt(II) nitrate, iron(III) nitrate, cobalt(III)nitrate, or any combination thereof; alternatively, iron(II) fluoride,iron(III) fluoride, iron(II) bromide, iron(III) bromide, iron(II)iodide, iron(III) iodide, iron(II) acetate, iron(III) acetate, iron(II)acetylacetonate, iron(III) acetylacetonate, iron(II) 2-ethylhexanoate,iron(III) 2-ethylhexanoate, iron(II) triflate, iron(III) triflate,iron(II) nitrate, iron(III) nitrate, or any combination thereof;alternatively, iron(II) chloride, cobalt(II) chloride, iron(III)chloride, cobalt(III) chloride, iron(II) acetate, cobalt(II) acetate,iron(III) acetate, cobalt(III) acetate, iron(II) acetylacetonate,cobalt(II) acetylacetonate, iron(III) acetylacetonate, cobalt(III)acetylacetonate, or any combination thereof; alternatively, iron(II)chloride, iron(III) chloride, iron(II) acetate, iron(III) acetate,iron(II) acetylacetonate, iron(III) acetylacetonate, or any combinationthereof; alternatively, iron(II) chloride, cobalt(II) chloride,iron(III) chloride, cobalt(III) chloride, iron(II) acetylacetonate,cobalt(II) acetylacetonate, iron(III) acetylacetonate, cobalt(III)acetylacetonate, or any combination thereof; alternatively, iron(II)chloride, iron(III) chloride, iron(II) acetylacetonate, iron(III)acetylacetonate, or any combination thereof; alternatively, iron(II)chloride; alternatively, iron(III) chloride; alternatively, iron(II)acetylacetonate; or alternatively, iron(III) acetylacetonate.

In some aspects, the heteroatomic ligand metal salt complex comprising aheteroatomic ligand complexed to a first metal salt can have a structureselected from the group consisting of

In other embodiments, the heteroatomic ligand metal salt complexcomprising a heteroatomic ligand complexed to a first metal salt can beselected from the group consisting of 2,6-bis[(phenylimine)methyl]pyridine iron dichloride,2,6-bis[(2-methylphenylimine)methyl]pyridine iron dichloride,2,6-bis[(2-ethylphenylimine)methyl]pyridine iron dichloride,2,6-bis[(2-isopropylphenylimine)methyl pyridine iron dichloride,2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine iron dichloride,2,6-bis[(2,6-diethylphenyl-imine)methyl]pyridine iron dichloride,2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)-methyl]pyridineiron dichloride,2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)-methyl]pyridineiron dichloride, and2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenyl-imine)methyl]pyridineiron dichloride. In other embodiments, the heteroatomic ligand metalsalt complex comprising a heteroatomic ligand complexed to a first metalsalt can be selected from the group consisting of2-[(2,6-difluorophenylimine)-1,10-phenanthroline iron dichloride,2-[(2,6-dichlorophenylimine)-1,10-phenanthroline iron dichloride,2-[(2,6-dibromophenylimine)-1,10-phenanthroline iron dichloride,2-[(2,6-dimethylphenylimine)-1,10-phenanthroline iron dichloride,2-[(2,6-diethylphenylimine)-1,10-phenanthroline iron dichloride,2-[(2,6-diisopropylphenylimine)-1,10-phenanthroline iron dichloride,2-[(2,6-difluorophenylimine)methyl]-1,10-phenanthroline iron dichloride,2-[(2,6-dichlorophenylimine)-methyl]-1,10-phenanthroline irondichloride, 2-[(2,6-dibromophenylimine)methyl]-1,10-phenanthroline irondichloride, 2-[(2,6-dimethylphenylimine)methyl]-1,10-phenanthroline irondichloride, 2-[(2,6-diethylphenylimine)methyl]-1,10-phenanthroline irondichloride, 2-[(2,6-diisopropylphenylimine)methyl]-1,10-phenanthrolineiron dichloride, 2-[(2,6-diethylphenylimine)ethyl]-1,10-phenanthrolineiron dichloride,2-[(2,6-diethylphenylimine)-n-propyl]-1,10-phenanthroline irondichloride, 2-[(2,6-diethylphenylimine)iso-propyl]-1,10-phenanthrolineiron dichloride,2-[(2,4,6-tribromophenylimine)methyl]-1,10-phenanthroline irondichloride, 2-[(2,4,6-trimethylphenylimine)methyl]-1,10-phenanthrolineiron dichloride,2-[(2,6-dimethyl-4bromophenylimine)methyl]-1,10-phenanthroline irondichloride,2-[(2,6-dibromo-4-methylphenylimine)methyl]-1,10-phenanthroline irondichloride,2-[(2,6-dibromo-chlorophenylimine)methyl]-1,10-phenanthroline irondichloride, 2-[(2,6-dimethylphenylimine)phenyl]-1,10-phenanthroline irondichloride, 2-[(2,6-diethylphenylimine)phenyl]-1,10-phenanthroline irondichloride, and2-[(2,6-diisopropylphenylimine)phenyl]-1,10-phenanthroline irondichloride.

It should be noted that while not explicitly shown or stated, the metalsalt, the heteroatomic ligand metal salt complex (comprising aheteroatomic ligand complexed to a first metal salt), and/or the secondmetal salt can further comprise a neutral ligand. While the neutralligand is not provided in the names, structures, or formulas providedherein, it should be understood that the metal salt, the heteroatomicligand metal salt complex (comprising a heteroatomic ligand complexed toa first metal salt), and/or the second metal salt names and depictionsdo not limit the metal salt, the heteroatomic ligand metal salt complex(comprising a heteroatomic ligand complexed to a first metal salt),and/or the second metal salt names and depictions to those not having aneutral ligand. In fact, the metal salt, the heteroatomic ligand metalsalt complex (comprising a heteroatomic ligand complexed to a firstmetal salt), and/or the second metal salt which can be utilized in anyaspect disclosed herein or any embodiment disclosed herein can include aneutral ligand and that these names and depictions provided herein donot limit the metal salt, the heteroatomic ligand metal salt complex(comprising a heteroatomic ligand complexed to a first metal salt),and/or the second metal salt to those which do not comprise a neutralligand regardless of the language utilized to describe the metal saltsor metal salt complexes. Neutral ligands are provided herein and can beutilized without limitation to further describe the metal salt, theheteroatomic ligand metal salt complex (comprising a heteroatomic ligandcomplexed to a first metal salt), and/or the second metal salt.

Generally, the neutral ligand, if present, can be any neutral ligandthat forms an isolatable compound with the metal salt, the heteroatomicligand metal salt complex (comprising a heteroatomic ligand complexed toa first metal salt), and/or the second metal salt. In an aspect, eachneutral ligand independently can be a nitrile, an ether, or an amine;alternatively, a nitrile; alternatively, an ether, or alternatively, anamine. The number of neutral ligands of the metal salt, the heteroatomicligand metal salt complex (comprising a heteroatomic ligand complexed toa first metal salt), and/or the second metal salt can be any number thatforms an isolatable compound with the metal salt and/or the heteroatomicligand metal salt complex. In an aspect, the number of neutral ligandsof the metal salt, the heteroatomic ligand metal salt complex(comprising a heteroatomic ligand complexed to a first metal salt),and/or the second metal salt can be 1, 2, 3, 4, 5, or 6; alternatively,1; alternatively, 2; alternatively, 3; alternatively, 4; alternatively,5; or alternatively, 6.

Generally, each nitrile ligand which can be utilized as the neutralligand independently can be a C₂ to C₂₀ nitrile; or alternatively, a C₂to C₁₀ nitrile. In an embodiment, each nitrile ligand independently canbe a C₂ to C₂₀ aliphatic nitrile, a C₇ to C₂₀ aromatic nitrile, a C₈ toC₂₀ aralkane nitrile, or any combination thereof; alternatively, a C₂ toC₂₀ aliphatic nitrile; alternatively, a C₇ to C₂₀ aromatic nitrile; oralternatively, a C₈ to C₂₀ aralkane nitrile. In some embodiments, eachnitrile ligand independently can be a C₂ to C₁₀ aliphatic nitrile, a C₇to C₁₀ aromatic nitrile, a C₈ to C₁₀ aralkane nitrile, or anycombination thereof; alternatively, a C₁ to C₁₀ aliphatic nitrile;alternatively, a C₇ to C₁₀ aromatic nitrile; or alternatively, a C₅ toC₁₀ aralkane nitrile. In an embodiment, each aliphatic nitrileindependently can be acetonitrile, propionitrile, a butyronitrile,benzonitrile, or any combination thereof; alternatively, acetonitrile;alternatively, propionitrile; alternatively, a butyronitrile; oralternatively, benzonitrile.

Generally, each ether ligand which can be utilized as the neutral ligandindependently can be a C₂ to C₄₀ ether, alternatively, a C₂ to C₃₀ether, or alternatively, a C₂ to C₂₀ ether. In an embodiment, each etherligand independently can be a C₂ to C₄₀ aliphatic ether, a C₃ to C₄₀aliphatic cyclic ether, a C₄ to C₄₀ aromatic cyclic ether,alternatively, a C₂ to C₄₀ aliphatic acyclic ether or a C₃ to C₄₀aliphatic cyclic ether; alternatively, a C₂ to C₄₀ aliphatic acyclicether, alternatively, a C₃ to C₄₀ aliphatic cyclic ether, oralternatively, a C₄ to C₄₀ aromatic cyclic ether. In some embodiments,each ether ligand independently can be a C₂ to C₃₀ aliphatic ether, a C₃to C₃₀ aliphatic cyclic ether, a C₄ to C₃₀ aromatic cyclic ether,alternatively, a C₂ to C₃₀ aliphatic acyclic ether or a C₃ to C₃₀aliphatic cyclic ether, alternatively, a C₂ to C₃₀ aliphatic acyclicether, alternatively, a C₃ to C₃₀ aliphatic cyclic ether, oralternatively, a C₄ to C₃₀ aromatic cyclic ether. In other embodiments,each ether ligand independently can be a C₂ to C₂₀ aliphatic ether, a C₃to C₂₀ aliphatic cyclic ether, a C₄ to C₂₀ aromatic cyclic ether,alternatively, a C₂ to C₂₀ aliphatic acyclic ether or a C₃ to C₂₀aliphatic cyclic ether; alternatively, a C₂ to C₂₀ aliphatic acyclicether, alternatively, a C₃ to C₂₀ aliphatic cyclic ether, oralternatively, a C₄ to C₂₀ aromatic cyclic ether. In some embodiments,each ether ligand independently can be dimethyl ether, diethyl ether, adipropyl ether, a dibutyl ether, methyl ethyl ether, a methyl propylether, a methyl butyl ether, tetrahydrofuran, a dihydrofuran,1,3-dioxolane, tetrahydropyran, a dihydropyran, a pyran, a dioxane,furan, benzofuran, isobenzofuran, isobenzofuran, dibenzofuran, diphenylether, a ditolyl ether, or any combination thereof; alternatively,dimethyl ether, diethyl ether, a dipropyl ether, a dibutyl ether, methylethyl ether, a methyl propyl ether, a methyl butyl ether, or anycombination thereof; alternatively, tetrahydrofuran, a dihydrofuran,1,3-dioxolane, tetrahydropyran, a dihydropyran, a pyran, a dioxane, orany combination thereof; alternatively furan, benzofuran, isobenzofuran,isobenzofuran, dibenzofuran, or any combination thereof; alternativelydiphenyl ether, a ditolyl ether, or any combination thereof;alternatively, dimethyl ether, alternatively, diethyl ether,alternatively, a dipropyl ether; alternatively, a dibutyl ether,alternatively, methyl ethyl ether; alternatively, a methyl propyl ether,alternatively, a methyl butyl ether, alternatively, tetrahydrofuran;alternatively, a dihydrofuran; alternatively, 1,3-dioxolane;alternatively, tetrahydropyran; alternatively, a dihydropyran;alternatively, a pyran; alternatively, a dioxane; alternatively, furan;alternatively, benzofuran; alternatively, isobenzofuran; alternatively,isobenzofuran; alternatively, dibenzofuran; alternatively, diphenylether; or alternatively, a ditolyl ether.

In an aspect, each amine ligand which can be utilized as thenon-α-diimine neutral ligand independently can be amonohydrocarbylamine, a dihydrocarbylamine, a trihydrocarbylamine, orany combination thereof; alternatively, a monohydrocarbylamine;alternatively, a dihydrocarbylamine; or alternatively, atrihydrocarbylamine. Monohydrocarbylamines which can be utilized as thenon-α-diimine neutral ligand can be a C₁ to C₃₀ monohydrocarbylamine, aC₁ to C₂₀ monohydrocarbylamine, a C₁ to C₁₀ monohydrocarbylamine, or aC₁ to C₅ monohydrocarbylamine. Dihydrocarbylamines which can be utilizedas the non-α-diimine neutral ligand can be a C₂ to C₃₀dihydrocarbylamine, a C₂ to C₂₀ dihydrocarbylamine, a C₂ to C₁₀dihydrocarbylamine, or a C₂ to C₅ dihydrocarbylamine.Trihydrocarbylamines which can be utilized as the non-α-diimine neutralligand can be a C₃ to C₃₀ trihydrocarbylamine, a C₃ to C₂₀trihydrocarbylamine, or a C₃ to C₁₀ trihydrocarbylamine. Hydrocarbylgroups (general and specific) are disclosed herein (e.g., as substituentgroups, among other places) and can be utilized without limitation tofurther describe the monohydrocarbylamines, dihydrocarbylamines, and/ortrihydrocarbylamines which can be utilized as the neutral ligand.Generally, each hydrocarbyl group of the dihydrocarbylamine (ortrihydrocarbylamine) is independent of each other and can be the same:or alternatively, can be different. In a non-limiting embodiment, themonohydrocarbylamine, which can be utilized as the non-α-diimine neutralligand can be, can comprise, or can consist essentially of, methylamine, ethyl amine, propyl amine, butyl amine, or any combinationthereof; alternatively, methyl amine; alternatively, ethyl amine;alternatively, propyl amine; or alternatively, butyl amine. In someembodiments, the dihydrocarbylamine, which can be utilized as thenon-α-diimine neutral ligand can be, can comprise, or can consistessentially of, dimethyl amine, diethyl amine, dipropyl amine,dibutylamine, or any combination thereof; alternatively, dimethyl amine;alternatively, diethyl amine; alternatively, dipropyl amine; oralternatively, dibutylamine. In some embodiments, thetrihydrocarbylamine, which can be utilized as the non-α-diimine neutralligand can be, can comprise, or can consist essentially of, trimethylamine, triethyl amine, tripropyl amine, tributyl amine, or anycombination thereof; alternatively, trimethyl amine; alternatively,triethyl amine; alternatively, tripropyl amine; or alternatively,tributyl amine.

In an aspect, the organoaluminum compound which can be utilized in theprocesses described herein can comprise an aluminoxane, an alkylaluminumcompound, or a combination thereof; alternatively, an aluminoxane; oralternatively, an alkylaluminum compound. In an aspect, thealkylaluminum compound can be a trialkylaluminum, an alkylaluminumhalide, an alkylaluminum alkoxide, or any combination thereof. In someaspects, the alkylaluminum compound can be a trialkylaluminum, analkylaluminum halide, or any combination thereof; alternatively, atrialkylaluminum, an alkylaluminum alkoxide, or any combination thereof;or alternatively, a trialkylaluminum. In other aspects, thealkylaluminum compound can be a trialkylaluminum; alternatively, analkylaluminum halide; or alternatively, an alkylaluminum alkoxide. In anembodiment, the organoaluminum compound (regardless of whether it is analuminoxane, an alkylaluminum compound, or subspecies or individualscontained therein) can be substantially devoid of (or alternatively,devoid of) β,δ-branched organyl groups (or alkyl group) and β,γ-branchedorganyl groups (or alkyl groups). Generally, substantially devoid ofβ,δ-branched organyl groups (or alkyl group) and β,γ-branched organylgroups (or alkyl group) can be taken to mean that less than 5, 4, 3, 2,1, 0.75, 0.5, 0.25, or 0.1 mole percent of the organoaluminum organylgroups are β,δ-branched organyl groups (or alkyl groups) andβ,γ-branched organyl groups (or alkyl groups).

In an aspect, each alkyl group of any organoaluminum compound or anyalkylaluminum compound disclosed herein (e.g., trialkylaluminum,alkylaluminum halide, alkylaluminum alkoxide or aluminoxane)independently can be a C₁ to C₂₀ alkyl group, a C₁ to C₁₀ alkyl group,or a C₁ to C₆ alkyl group. In an aspect, each alkyl group of anyorganoaluminum compound or any alkylaluminum compound disclosed herein(e.g., trialkylaluminum, alkylaluminum halide, alkylaluminum alkoxide,or aluminoxane) independently can be a methyl group, an ethyl group, apropyl group, a butyl group, a pentyl group, a hexyl group, a heptylgroup, or an octyl group; alternatively, a methyl group, an ethyl group,a butyl group, a hexyl group, or an octyl group. In some aspects, eachalkyl group of any organoaluminum compound or any alkylaluminum compounddisclosed herein (e.g., trialkylaluminum, alkylaluminum halide,alkylaluminum alkoxide or aluminoxane) independently can be a methylgroup, an ethyl group, an n-propyl group, an n-butyl group, an iso-butylgroup, an n-hexyl group, or an n-octyl group; alternatively, a methylgroup, an ethyl group, an n-butyl group, or an iso-butyl group;alternatively, a methyl group; alternatively, an ethyl group;alternatively, an n-propyl group; alternatively, an n-butyl group;alternatively, an iso-butyl group; alternatively, an n-hexyl group; oralternatively, an n-octyl group. In an embodiment, the organoaluminumcompound (regardless of whether it is an aluminoxane, an alkylaluminumcompound, or a subspecies or individuals contained therein) can besubstantially devoid (or alternatively, devoid of) of β,δ-branched alkylgroups and β,γ-branched alkyl groups. Generally, substantially devoid ofβ,δbranched alkyl groups and β,γ-branched alkyl groups can be taken tomean that less than 5, 4, 3, 2, 1, 0.75, 0.5, 0.25, or 0.1 mole percentof the alkyl groups are β,δ-branched alkyl groups and β,γ-branched alkylgroups.

In an aspect, each halide of any alkylaluminum halide disclosed hereinindependently can be chloride, bromide, or iodide. In some aspects, eachhalide of any alkylaluminum halide disclosed herein can be chloride orbromide; or alternatively, chloride.

In an aspect, each alkoxide group of any alkylaluminum alkoxidedisclosed herein independently can be a C₁ to C₂₀ alkoxy group, a C₁ toC₁₀ alkoxy group, or a C₁ to C₆ alkoxy group. In an aspect, eachalkoxide group of any alkylaluminum alkoxide disclosed hereinindependently can be a methoxy group, an ethoxy group, a propoxy group,a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, or anoctoxy group; alternatively, a methoxy group, an ethoxy group, a butoxygroup, a hexoxy group, or an octoxy group. In some aspects, eachalkoxide group of any alkylaluminum alkoxide disclosed hereinindependently can be a methoxy group, an ethoxy group, an n-propoxygroup, an n-butoxy group, an iso-butoxy group, an n-hexoxy group, or ann-octoxy group; alternatively, a methoxy group, an ethoxy group, ann-butoxy group, or an iso-butoxy group; alternatively, a methoxy group;alternatively, an ethoxy group; alternatively, an n-propoxy group;alternatively, an n-butoxy group; alternatively, an iso-butoxy group;alternatively, an n-hexoxy group; or alternatively, an n-octoxy group.

In a non-limiting aspect, the trialkylaluminum compound can comprise,can consist essentially of, or can be, trimethylaluminum,triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum,trioctylaluminum, or mixtures thereof. In some non-limiting aspects, thetrialkylaluminum compound can comprise, can consist essentially of, orcan be, trimethylaluminum, triethylaluminum, tripropylaluminum,tri-n-butylaluminum, tri-isobutylaluminum, trihexylaluminum,tri-n-octylaluminum, or mixtures thereof; alternatively,triethylaluminum, tri-n-butylaluminum, tri-isobutylaluminum,trihexylaluminum, tri-n-octylaluminum, or mixtures thereof;alternatively, triethylaluminum, tri-n-butylaluminum, trihexylaluminum,tri-n-octylaluminum, or mixtures thereof. In other non-limiting aspects,the trialkylaluminum compound can comprise, can consist essentially of,or can be, trimethylaluminum; alternatively, triethylaluminum;alternatively, tripropylaluminum; alternatively, tri-n-butylaluminum;alternatively, tri-isobutylaluminum; alternatively, trihexylaluminum; oralternatively, tri-n-octylaluminum.

In a non-limiting aspect, the alkylaluminum halide can comprise, canconsist essentially of, or can be, diethylaluminum chloride,diethylaluminum bromide, ethylaluminum dichloride, ethylaluminumsesquichloride, and mixtures thereof. In some non-limiting aspects, thealkylaluminum halide can comprise, can consist essentially of, or can bediethylaluminum chloride, ethylaluminum dichloride, ethylaluminumsesquichloride, and mixtures thereof; or alternatively, diethylaluminumchloride; alternatively, diethylaluminum bromide; alternatively,ethylaluminum dichloride; or alternatively, ethylaluminumsesquichloride.

In a non-limiting aspect, the aluminoxane can have a repeating unitcharacterized by the Formula I:

wherein R′ is a linear or branched alkyl group. Alkyl groups fororganoaluminum compounds are independently described herein and can beutilized without limitation to further describe the aluminoxanes havingFormula I. Generally, n of Formula I is greater than 1; oralternatively, greater than 2. In an aspect, n can range from 2 to 15;or alternatively, from 3 to 10. In an embodiment, R′ of the aluminoxanecan be substantially devoid (or alternatively, devoid of) ofβ,δ-branched alkyl groups and β,γ-branched alkyl groups. Generally,substantially devoid of β,δ-branched alkyl groups and β,γ-branched alkylgroups can be taken to mean that less than 5, 4, 3, 2, 1, 0.75, 0.5,0.25, or 0.1 mole percent of the aluminoxane alkyl groups areβ,δ-branched alkyl groups and β,γ-branched alkyl groups.

In a non-limiting aspect, the aluminoxane can be a reaction product ofwater with an organoaluminum compound. In some embodiments, theorganoaluminum compound can have the formula AlR^(Al) _(x)H_(3-x) wherex is an integer from 1 to 3 and each R can be any organyl group,hydrocarbyl group, or alkyl group (alternatively, any organyl group;alternatively, any hydrocarbyl groups; or alternatively, any alkylgroup) of the organoaluminum compounds disclosed herein. In somenon-limiting embodiments, the organoaluminum having the formula AlR^(Al)_(x)H_(3-x), of the aluminoxane which can be a reaction product of waterwith an organoaluminum compound having the formula AlR^(Al) _(x)H_(3-x),is substantially devoid of (or alternatively, devoid of) β,δ-branchedand β,γ-branched R^(A1) groups. Generally, substantially devoid ofβ,δ-branched and β,γ-branched R^(A1) groups can be taken to mean thatless than 5, 4, 3, 2, 1, 0.75, 0.5, 0.25, or 0.1 mole percent of theR^(A1) groups are β,δ-branched and β,γ-branched R^(A1) groups, organylgroups, hydrocarbyl groups, and/or alkyl group; alternatively, organylgroups; alternatively, hydrocarbyl groups; or alternatively, alkylgroups.

In a non-limiting aspect, the aluminoxane can comprise, can consistessentially of, or can be, methylaluminoxane (MAO), ethylaluminoxane,modified methylaluminoxane (MMAO), n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane,iso-butylaluminoxane, t-butylaluminoxane, 1-pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane,neopentylaluminoxane, or mixtures thereof. In some non-limiting aspects,the aluminoxane can comprise, can consist essentially of, or can be,methylaluminoxane (MAO), a modified methylaluminoxane (MMAO),isobutylaluminoxane, t-butylaluminoxane, or mixtures thereof. In othernon-limiting aspects, the aluminoxane can be, comprise, or consistessentially of, methylaluminoxane (MAO); alternatively,ethylaluminoxane; alternatively, modified methylaluminoxane (MMAO);alternatively, n-propylaluminoxane; alternatively,iso-propylaluminoxane; alternatively, n-butylaluminoxane; alternatively,sec-butylaluminoxane; alternatively, iso-butylaluminoxane;alternatively, t-butylaluminoxane; alternatively, 1-pentylaluminoxane;alternatively, 2-pentylaluminoxane; alternatively, 3-pentylaluminoxane;alternatively, iso-pentylaluminoxane; or alternatively,neopentylaluminoxane. In an embodiment, the aluminoxane can besubstantially devoid (or alternatively, devoid of) of β,δ-branched alkylgroups and β,γ-branched alkyl groups. Generally, a aluminoxanesubstantially devoid of β,δ-branched alkyl groups and β,γ-branched alkylgroups can be taken to mean that less than 5, 4, 3, 2, 1, 0.75, 0.5,0.25, or 0.1 mole percent of the aluminoxane alkyl groups areβ,δ-branched alkyl groups and β,γ-branched alkyl groups.

In an aspect, the processes described herein can utilize an organicreaction medium. Generally, the organic reaction medium can act as asolvent and/or a diluent in the processes described herein. In anaspect, the organic reaction medium can comprise, can consistessentially of, or can be, a hydrocarbon, a halogenated hydrocarbon, ora combination thereof; alternatively, a hydrocarbon; or alternatively, ahalogenated hydrocarbon(s). In an aspect, hydrocarbons which can beutilized as the organic reaction medium can be an aliphatic hydrocarbon,an aromatic hydrocarbon, or any combination thereof; alternatively, analiphatic hydrocarbon; or alternatively, an aromatic hydrocarbon. Insome aspects, the aliphatic hydrocarbon which can be utilized as theorganic reaction medium can comprise, can consist essentially of, or canbe, a saturated aliphatic hydrocarbon, an olefinic aliphatichydrocarbon, or any combination thereof; alternatively, a saturatedaliphatic hydrocarbon(s); or alternatively an olefinic aliphatichydrocarbon(s). In an aspect, halogenated hydrocarbons which can beutilized as the organic reaction medium can be a halogenated aliphatichydrocarbon, a halogenated aromatic hydrocarbon, or any combinationthereof; alternatively, a halogenated aliphatic hydrocarbon; oralternatively, a halogenated aromatic hydrocarbon.

In an aspect, the hydrocarbon, aliphatic hydrocarbon, saturatedaliphatic hydrocarbon, or olefinic aliphatic hydrocarbon which can beutilized as the organic reaction medium can comprise, consistessentially of, or can be, a C₃ to C₁₈, a C₄ to C₁₈, or a C₅ to C₁₀hydrocarbon(s), aliphatic hydrocarbon(s), saturated aliphatichydrocarbon(s), or olefinic aliphatic hydrocarbon(s). In other aspects,the aliphatic hydrocarbon(s) (saturated or olefinic) which can useful asan organic reaction medium can comprise, can consist essentially of, orcan be, a C₈ to C₁₈, a C₈ to C₁₆, or alternatively, a C₁₀ to C₁₄hydrocarbon(s), aliphatic hydrocarbon(s), saturated aliphatichydrocarbon(s), or olefinic aliphatic hydrocarbon(s). Thehydrocarbon(s), aliphatic hydrocarbon(s), saturated aliphatichydrocarbon(s), or olefinic hydrocarbon(s) can be cyclic or acyclicand/or can be linear or branched, unless otherwise specified.

Non-limiting examples of suitable hydrocarbon organic reaction mediumsthat can be utilized singly or in any combination include propane,butane(s), pentane(s), hexane(s), heptane(s), octane(s), decane(s),undecane(s), dodecane(s), tridecane(s), tetradecane(s), pentadecane(s),hexadecane(s), heptadecane(s), octadecane(s), hexene(s), heptene(s),octene(s), nonene(s), decene(s), dodecene(s), tetradecene(s),hexadecene(s), octadecene(s), or any combination thereof; alternatively,propane, butane(s), pentane(s), hexane(s), heptane(s), octane(s),decane(s), undecane(s), dodecane(s), tridecane(s), tetradecane(s),pentadecane(s), hexadecane(s), heptadecane(s), octadecane(s), or anycombination thereof; or alternatively, hexene(s), heptene(s), octene(s),nonene(s), decene(s), dodecene(s), tetradecene(s), hexadecene(s),octadecene(s), or any combination thereof. In an aspect, suitableacyclic aliphatic hydrocarbon organic reaction mediums that can beutilized can comprise, or can consist essentially of, propane,iso-butane, n-butane, butane (n-butane or a mixture of linear andbranched C₄ acyclic aliphatic hydrocarbons), pentane (n-pentane or amixture of linear and branched C₅ acyclic aliphatic hydrocarbons),hexane (n-hexane or mixture of linear and branched C₆ acyclic aliphatichydrocarbons), heptane (n-heptane or mixture of linear and branched C₇acyclic aliphatic hydrocarbons), octane (n-octane or a mixture of linearand branched C₈ acyclic aliphatic hydrocarbons), or any combinationthereof. In another aspect, a saturated aliphatic hydrocarbon cancomprise, or consist essentially of 1-octane, 1-decane, 1-dodecane,1-tetradecane, 1-hexadecane, 1-octadecane, or any combination thereof;alternatively, 1-decane, 1-dodecane, 1-tetradecane, or any combinationthereof; alternatively, 1-decane; alternatively, 1-dodecane; oralternatively, 1-tetradecane. In an aspect, an olefinic aliphatichydrocarbon which can be utilized as the organic reaction medium cancomprise, can consist essentially of, or can be, an alpha olefin(s); oralternatively, a normal alpha olefin(s). In a non-limiting aspect, theolefinic aliphatic hydrocarbon which can be utilized as the organicreaction medium can be, can comprise, or can consist essentially of,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, or any combination thereof; alternatively, 1-decene,1-dodecene, 1-tetradecene, or any combination thereof; alternatively,1-decene; alternatively, 1-dodecene; or alternatively, 1-tetradecene. Ina non-limiting aspect, the cyclic aliphatic hydrocarbon(s) which can beused as an organic reaction medium can comprise, or consist essentiallyof cyclohexane, methyl cyclohexane, or any combination thereof.

Non-limiting examples of suitable aromatic hydrocarbon(s) which can beused as an organic reaction medium can comprise, or can consistessentially of, a C₆ to C₁₀ aromatic hydrocarbon(s). In a non-limitingaspect, the aromatic hydrocarbon(s) which can be utilized as the organicreaction medium can comprise, or can consist essentially of benzene,toluene, xylene (including ortho-xylene, meta-xylene, para-xylene, ormixtures thereof), ethylbenzene, or combinations thereof.

Non-limiting examples of the halogenated aliphatic hydrocarbon(s) whichcan be used as the organic reaction medium can comprise, or can consistessentially of, a C₁ to C₁₅ halogenated aliphatic hydrocarbon(s), a C₁to C₁₀ halogenated aliphatic hydrocarbon(s), or a C₁ to C₅ halogenatedaliphatic hydrocarbon(s). The halogenated aliphatic hydrocarbon(s) whichcan be utilized as an organic reaction medium can be cyclic or acyclicand/or can be linear or branched, unless otherwise specified. In anon-limiting aspect, the halogenated aliphatic hydrocarbon(s) which canbe utilized as an organic reaction medium can comprise, or can consistessentially of methylene chloride, chloroform, carbon tetrachloride,dichloroethane, trichloroethane, or combinations thereof.

Non-limiting examples of the halogenated aromatic hydrocarbon(s) whichcan be useful as the organic reaction medium can comprise, or canconsist essentially of, a C₆ to C₂₀ halogenated aromatic hydrocarbon(s),or a C₆ to C₁₀ halogenated aromatic hydrocarbon(s). In a non-limitingaspect, the halogenated aromatic hydrocarbon(s) which can be used as theorganic reaction medium can comprise, or can consist essentially of,chlorobenzene, dichlorobenzene, or any combination thereof.

The choice of organic reaction medium can be made on the basis ofconvenience in processing. For example, isobutane can be chosen to becompatible with solvents and diluents used in processes using theproduct(s) of the processes described herein (e.g., using the productfor the formation of polymer in a subsequent processing step). In someaspects, the organic reaction medium can be chosen to be easilyseparable from the one or more oligomers in the oligomer product. Insome aspects, an oligomer of the oligomer product can be utilized as thereaction system solvent.

In an aspect, the oligomer product can be formed in a reaction zone. Inan embodiment, the reaction zone of any process described herein cancomprise a continuous stirred tank reactor, a plug flow reactor, or anycombination thereof; alternatively, a continuous stirred tank reactor,or alternatively, a plug flow reactor. In some embodiments, the reactionzone of any process described herein can comprise a continuous stirredtank reactor, a loop reactor, a solution reactor, a tubular reactor, arecycle reactor, a bubble reactor, or any combination thereof;alternatively, a continuous stirred tank reactor, alternatively, a loopreactor; alternatively, a solution reactor, alternatively, a tubularreactor; alternatively, a recycle reactor; or alternatively, a bubblereactor. In other embodiments, the reaction zone in which the oligomerproduct can be formed can comprise multiple reactors; or alternatively,only one reactor. When multiple reactors are present, each of thereactors can be the same or can be different types of reactors.Additionally, when the reaction zone can comprise more than one reactor,each reactor independently can be any reactor described herein, and thereactors can be arranged in series, parallel, or any combinationthereof; alternatively, in series; or alternatively, in parallel.

It should be noted that when the reaction zone can comprise multiplereactors, each reactor can be operated independent of each other(regardless of whether they are operated in series or parallel). Assuch, the contact modes (if needed), the conditions under which theoligomer product can be formed, the oligomer product formationparameters under which the oligomer product can be formed, and/or thereaction zone conditions can be different for each reactor. Inparticular, when the reaction zone comprises multiple reactors inseries, each reactor can be operated to achieve different goals. Forexample, a first reactor can be operated to i) contact ethylene, themetal salt and the heteroatomic ligand (or alternatively, ethylene, thefirst metal salt, and the heteroatomic ligand complexed to the firstmetal salt), the optional organic reaction medium and the optionalhydrogen and ii) initiate production of the oligomer product under afirst set of conditions capable of producing the oligomer product tosome intermediate ethylene conversion and the effluent of the firstreactor transferred to a second reactor operated to achieve the desiredethylene conversion under a second set of conditions capable ofproducing the oligomer product with or without additional ethylene, themetal salt, the heteroatomic ligand (or alternatively, ethylene, thefirst metal salt, and the heteroatomic ligand complexed to the firstmetal salt), the optional organic reaction medium and the optionalhydrogen being added to the reactor/reaction zone.

In any aspect and/or embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at,conditions that can comprise, either singly or in any combination, aheteroatomic ligand molar equivalent concentration, a heteroatomicligand first metal salt complex molar equivalent concentration, anequivalent molar ratio of second metal salt to heteroatomic ligand ofthe heteroatomic ligand metal salt complex, an equivalent molar ratio ofsecond metal salt to heteroatomic ligand metal salt complex, anequivalent molar ratio of metal salt to heteroatomic ligand, an aluminumof the organoaluminum compound to heteroatomic ligand molar equivalentratio, an aluminum of the organoaluminum compound to heteroatomic ligandfirst metal salt complex molar equivalent ratio, an aluminum of theorganoaluminum compound concentration, an ethylene partial pressure, anethylene to organic reaction medium mass ratio, a temperature (or anaverage temperature), an Schulz-Flory K value, a hydrogen partialpressure, and/or a hydrogen to ethylene mass ratio. In any aspect and/orembodiment, the oligomer product can be formed at, the reaction zone canhave, or the reaction zone can operate at, conditions that can comprise,a heteroatomic ligand molar equivalent concentration; alternatively, aheteroatomic ligand first metal salt complex molar equivalentconcentration; alternatively, an equivalent molar ratio of second metalsalt to heteroatomic ligand of the heteroatomic ligand metal saltcomplex; alternatively, an equivalent molar ratio of second metal saltto heteroatomic ligand metal salt complex; alternatively, an equivalentmolar ratio of metal salt to heteroatomic ligand; alternatively, analuminum of the organoaluminum compound to heteroatomic ligand molarequivalent ratio; alternatively, an aluminum of the organoaluminumcompound to heteroatomic ligand first metal salt complex molarequivalent ratio; alternatively, an aluminum of the organoaluminumcompound concentration; alternatively, an ethylene partial pressure;alternatively, an ethylene to organic reaction medium mass ratio;alternatively, a temperature (or an average temperature); alternatively,an Schulz-Flory K value; alternatively, a hydrogen partial pressure; oralternatively, a hydrogen to ethylene mass ratio.

In any aspect and/or embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at, aparticular heteroatomic ligand molar equivalent concentration (oralternatively, heteroatomic ligand metal salt complex molar equivalentconcentration). In an embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at, aminimum heteroatomic ligand molar equivalent concentration (oralternatively, heteroatomic ligand metal salt complex molar equivalentconcentration) of 1×10⁻⁶, 1×10⁻⁵, or 1×10⁻⁴ heteroatomic ligand molarequivalents/kg (or alternatively, heteroatomic ligand metal salt complexmolar equivalents/kg) based upon the kg mass of the reaction solution;alternatively or additionally, at a maximum heteroatomic ligand molarequivalent concentration (or alternatively, heteroatomic ligand metalsalt complex molar equivalent concentration) of 1×10⁻¹, 1×10⁻², or1×10⁻³ heteroatomic ligand molar equivalents/kg (or alternatively,heteroatomic ligand metal salt complex molar equivalents/kg) based uponthe kg mass of the reaction solution. In an aspect, the oligomer productcan be formed at, the reaction zone can have, or the reaction zone canoperate at, a heteroatomic ligand molar equivalent concentration (oralternatively, heteroatomic ligand metal salt complex molar equivalentconcentration) in the range of any minimum heteroatomic ligand molarequivalent concentration (or alternatively, heteroatomic ligand metalsalt complex molar equivalent concentration) disclosed herein to anymaximum heteroatomic ligand molar equivalent concentration (oralternatively, heteroatomic ligand metal salt complex molar equivalentconcentration) disclosed herein. In a non-limiting embodiment, theoligomer product can be formed, the reaction zone can have, or thereaction zone can operate, at an heteroatomic ligand molar equivalentconcentration (or alternatively, heteroatomic ligand metal salt complexmolar equivalent concentration) in the range of 1×10⁻⁶ to 1×10⁻¹, 1×10⁻⁵to 1×10⁻², or 1×10⁻⁴ to 1×10⁻³ heteroatomic ligand molar equivalents/kg(or alternatively, heteroatomic ligand metal salt complex molarequivalents/kg) based upon the kg mass of the reaction solution. Otherheteroatomic ligand molar equivalent concentration (or alternatively,heteroatomic ligand metal salt complex molar equivalent concentration)ranges that can be utilized are readily apparent to those skilled in theart with the aid of this disclosure.

In any aspect and/or embodiment utilizing a second metal salt and aheteroatomic ligand first metal salt complex, the oligomer product canbe formed at, the reaction zone can have, or the reaction zone canoperate at, a particular equivalent molar ratio of the second metal saltto the heteroatomic ligand of the heteroatomic ligand metal salt complex(or a particular equivalent molar ratio of the second metal salt to theheteroatomic ligand first metal salt complex). In an embodiment, theoligomer product can be formed at, the reaction zone can have, or thereaction zone can operate at, a minimum equivalent molar ratio of thesecond metal salt to the heteroatomic ligand of the heteroatomic ligandfirst metal salt complex (or a minimum equivalent molar ratio of thesecond metal salt to the heteroatomic ligand first metal salt complex)of 0.1:1, 0.25:1, 0.5:1, 1.2:1, 2:1, or 3:1; alternatively oradditionally, a maximum equivalent molar ratio of the second metal saltto the heteroatomic ligand of the heteroatomic ligand first metal saltcomplex (or a maximum equivalent molar ratio of the second metal salt tothe heteroatomic ligand first metal salt complex) of 100:1, 50:1, 25:1,17:1 or 10:1. In an embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at, anequivalent molar ratio of the second metal salt to heteroatomic ligandof the heteroatomic ligand first metal salt complex (or an equivalentmolar ratio of the second metal salt to the heteroatomic ligand firstmetal salt complex) in the range of any minimum equivalent molar ratioof the second metal salt to the heteroatomic ligand of the heteroatomicligand first metal salt complex (or a minimum equivalent molar ratio ofthe second metal salt to the heteroatomic ligand first metal saltcomplex) disclosed herein to any maximum equivalent molar ratio of thesecond metal salt to the heteroatomic ligand of the heteroatomic ligandfirst metal salt complex (or maximum equivalent molar ratio of thesecond metal salt to the heteroatomic ligand first metal salt complex)disclosed herein. In a non-limiting embodiment, the equivalent molarratio of the second metal salt to heteroatomic ligand of theheteroatomic ligand first salt complex (or equivalent molar ratio of thesecond metal salt to the heteroatomic ligand first metal salt complex)can be in the range of from 0.1:1 to 100:1, from 0.25:1 to 50:1, from0.5:1 to 50:1, from 1.2:1 to 50:1, from 1.2:1 to 25:1; from 2:1 to 17:1,or from 3:1 to 10:1. Other ranges of the equivalent molar ratio ofsecond metal salt to heteroatomic ligand of the heteroatomic ligandfirst metal salt complex iron salt (or equivalent molar ratio of thesecond metal salt to the heteroatomic ligand first metal salt complex)that can be utilized will be readily apparent to those skilled in theart with the aid of this disclosure.

In any aspect and/or embodiment utilizing a metal salt and aheteroatomic ligand, the oligomer product can be formed at, the reactionzone can have, or the reaction zone can operate at, a particularequivalent molar ratio of the metal salt to heteroatomic ligand. In anembodiment, the oligomer product can be formed at, the reaction zone canhave, or the reaction zone can operate at, a minimum equivalent molarratio of the metal salt to heteroatomic ligand of 1.25:1, 1.5:1, 2:1,2.5:1 or 3:1; alternatively or additionally, a maximum equivalent molarratio of iron salt to heteroatomic ligand of 100:1, 75:1 50:1, 40:1,30:1, 25:1, 20:1, 15:1, or 10:1. In an embodiment, the oligomer productcan be formed at, the reaction zone can have, or the reaction zone canoperate at, an equivalent molar ratio of the metal salt to heteroatomicligand in the range of any minimum equivalent molar ratio of the metalsalt to heteroatomic ligand disclosed herein to any maximum equivalentmolar ratio of the metal salt to heteroatomic ligand disclosed herein.In a non-limiting embodiment, the equivalent molar ratio of the metalsalt to heteroatomic ligand can be in the range of from 1.25 to 100:1,from 1.5 to 75:1, from 1.5 to 50:1, from 1.5:1 to 40:1; from 2:1 to40:1, from 2.5:1 to 40:1, from 3:1 to 30:1, from 3:1 to 25:1, from 3:1to 20:1, from 3:1 to 15:1, or from 3:1 to 10:1. Other ranges of theequivalent molar ratio of the metal salt to heteroatomic ligand that canbe utilized will be readily apparent to those skilled in the art withthe aid of this disclosure.

In any aspect and/or embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at aparticular aluminum of the organoaluminum compound to heteroatomicligand molar equivalent ratio (or alternatively, aluminum of theorganoaluminum compound to heteroatomic ligand first metal salt complexmolar equivalent ratio). In an embodiment, the oligomer product can beformed at, the reaction zone can have, or the reaction zone can operateat, a minimum aluminum of the organoaluminum compound to heteroatomicligand molar equivalent ratio (or alternatively, aluminum of theorganoaluminum compound to heteroatomic ligand first metal salt complexmolar equivalent ratio), of 100:1, 200:1, 300:1, or 400:1; alternativelyor additionally, a maximum aluminum of the organoaluminum compound toheteroatomic ligand molar equivalent ratio (or alternatively, aluminumof the organoaluminum compound to heteroatomic ligand first metal saltcomplex molar equivalent ratio), of 5,000:1, 2,000:1, 1,500:1, or1,000:1. In an embodiment, the oligomer product can be formed at, thereaction zone can have, or the reaction zone can operate at, an aluminumof the organoaluminum compound to heteroatomic ligand molar equivalentratio (or alternatively, aluminum of the organoaluminum compound toheteroatomic ligand first metal salt complex molar equivalent ratio), inthe range of any minimum aluminum of the organoaluminum compound toheteroatomic ligand molar equivalent ratio (or alternatively, aluminumof the organoaluminum compound to heteroatomic ligand first metal saltcomplex molar equivalent ratio), disclosed herein to any maximumaluminum of the organoaluminum compound to heteroatomic ligand molarequivalent ratio (or alternatively, aluminum of the organoaluminumcompound to heteroatomic ligand first metal salt complex molarequivalent ratio), disclosed herein. In a non-limiting embodiment, theoligomer product can be formed at, the reaction zone can have, or thereaction zone can operate at, an aluminum of the organoaluminum compoundto heteroatomic ligand molar equivalent ratio (or alternatively,aluminum of the organoaluminum compound to heteroatomic ligand firstmetal salt complex molar equivalent ratio), in the range of 100:1 to5,000:1, 200:1 to 2,000:1, 300:1 to 1,500:1, or 400:1 to 1,000:1. Otheraluminum of the organoaluminum compound to heteroatomic ligand molarequivalent ratio (or alternatively, aluminum of the organoaluminumcompound to heteroatomic ligand first metal salt complex molarequivalent ratio), ranges that can be utilized are readily apparent tothose skilled in the art with the aid of this disclosure.

In any aspect and/or embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at, aparticular aluminum of the organoaluminum compound concentration, alsoreferred to as aluminum concentration or Al concentration. In anembodiment, the oligomer product can be formed at, the reaction zone canhave, or the reaction zone can operate at, a minimum Al concentration of0.3 mmol Al/kg, 0.75 mmol Al/kg, 0.9 mmol Al/kg, or 1.1 mmol Al/kg basedupon the kg mass of the reaction solution; alternatively oradditionally, a maximum Al concentration of 15 mmol Al/kg, 12.5 mmolAl/kg, 10 mmol Al/kg, 7.5 mmol Al/kg, 5 mmol Al/kg, 2.6 mmol Al/kg, 2.2mmol Al/kg, 1.8 mmol Al/kg, or 1.5 mmol Al/kg based upon the kg mass ofthe reaction solution. In an embodiment, the oligomer product can beformed at, the reaction zone can have, or the reaction zone can operateat, an Al concentration in the range of any minimum Al concentrationdisclosed herein to any maximum Al concentration disclosed herein. In anon-limiting embodiment, the oligomer product can be formed at, thereaction zone can have, or the reaction zone can operate at, an Alconcentration in the range of 0.3 mmol Al/kg to 15 mmol Al/kg, 0.3 mmolAl/kg to 10 mmol Al/kg, 0.5 mmol Al/kg to 10 mmol Al/kg, 0.5 mmol Al/kgto 7.5 mmol Al/kg, 0.5 mmol Al/kg to 5 mmol Al/kg, 0.75 mmol Al/kg to2.6 mmol Al/kg, 0.75 mmol Al/kg to 2.2 mmol Al/kg, 0.9 mmol Al/kg to 1.8mmol Al/kg, 1.1 mmol Al/kg to 1.8 mmol Al/kg, or 1.1 mmol Al/kg to 1.5mmol Al/kg based upon the kg mass of the reaction solution. Other Alconcentration ranges that can be utilized are readily apparent to thoseskilled in the art with the aid of this disclosure.

In any aspect and/or embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at, aminimum ethylene partial pressure of 50 psi (344 KPa), 100 psi (689KPa), 250 psi (1.72 MPa), 500 psi (3.45 MPa), or 800 psi (5.52 MPa);alternatively or additionally, a maximum ethylene partial pressure of5,000 psi (34.5 MPa), 3,000 psi (20.9 MPa), 2,000 psi (13.8 MPa), 1,500psi (10.3 MPa), or 1000 psi (6.89 MPa). In an embodiment, the oligomerproduct can be formed at, the reaction zone can have, or the reactionzone can operate at, an ethylene partial pressure in the range of anyminimum ethylene partial pressure disclosed herein to any maximumethylene partial pressure disclosed herein. In some non-limitingembodiments, the oligomer product can be formed at, the reaction zonecan have, or the reaction zone can operate at, an ethylene partialpressure in the range of 50 psi (344 KPa) to 5,000 psi (34.5 MPa), 100psi (689 KPa) to 3,000 psi (20.9 MPa), 250 psi (1.72 MPa) to 2,000 psi(13.8 MPa), 500 psi (3.45 MPa) to 2,000 psi (13.8 MPa), 500 psi (3.45MPa) to 1,500 psi (10.3 MPa), or 800 psi (5.52 kPa) to 1000 psi (6.89MPa). Other ethylene partial pressure ranges are readily apparent tothose skilled in the art with the aid of this disclosure.

In any aspect and/or embodiment wherein an organic reaction medium isutilized, the oligomer product can be formed at, the reaction zone canhave, or the reaction zone can operate at, a minimum ethylene:organicreaction medium mass ratio of 0.8:1, 1:1, 1.25:1, or 1.5:1;alternatively, or additionally, a maximum ethylene:organic reactionmedium mass ratio of 4.5:1, 4:1, 3.5:1, 3:1, or 2.5:1. In an embodimentwherein an organic reaction medium is utilized, the oligomer product canbe formed at, the reaction zone can have, or the reaction zone canoperate at, an ethylene:organic reaction medium mass ratio in the rangeof any minimum ethylene:organic reaction medium mass ratio disclosedherein to any maximum ethylene:organic reaction medium mass ratiodisclosed herein. In some non-limiting embodiments wherein an organicreaction medium is utilized, the oligomer product can be formed at, thereaction zone can have, or the reaction zone can operate at, anethylene:organic reaction medium mass ratio in the range of 0.8:1 to4.5:1, 1:1 to 4:1, 1:1 to 3.5:1, 1.25:1 to 3:1, or 1.5:1 to 2.5:1. Otherethylene:organic reaction medium mass ratio ranges that can be utilizedare readily apparent to those skilled in the art with the aid of thisdisclosure.

In any aspect and/or embodiment, the oligomer product can be formed at,the reaction zone can have, or the reaction zone can operate at, aminimum reaction zone temperature of 0° C., 25° C., 40° C., 50° C., or60° C.; alternatively or additionally, a maximum reaction zone reactionzone temperature of 200° C., 150° C., 125° C., 110° C., or 100° C. In anembodiment, the oligomer product can be formed at, the reaction zone canhave, or the reaction zone can operate at, a reaction zone temperaturein the range of any minimum temperature disclosed herein to any maximumtemperature disclosed herein. In a non-limiting embodiment, the oligomerproduct can be formed at, the reaction zone can have, or the reactionzone can operate at, a reaction zone temperature in the range of 0° C.to 200° C., 25° C. to 150° C., 40° C. to 125° C., 50° C. to 125° C., 50°C. to 110° C., or 60° C. to 100° C. Other temperature ranges that can beutilized are readily apparent to those skilled in the art with the aidof this disclosure. In embodiments where the temperature can vary withinthe reaction zone, the temperatures provided herein accordingly can beaverage minimum reaction zone temperatures, average maximum reactionzone temperatures, or average reaction zone temperature.

In any aspect and/or aspect embodiment, the oligomer product can have aminimum Schulz-Flory K value of 0.4, 0.45, 0.5 or, 0.55; alternativelyor additionally, a maximum Schulz-Flory K value of 0.9, 0.85, 0.8, 0.75,0.7 or, 0.65. In an embodiment, the oligomer product can have aSchulz-Flory K value in the range of any minimum Schulz-Flory K valuedisclosed herein to any maximum Schulz-Flory K value disclosed herein.For example, in some non-limiting embodiments, the oligomer product canhave a Schulz-Flory K value in the range from 0.4 to 0.9; alternatively,from 0.4 to 0.8; alternatively, from 0.5 to 0.8; alternatively, from 0.5to 0.7; alternatively, from 0.55 to 0.7. Other oligomer productSchulz-Flory K value ranges are readily apparent to those of ordinaryskill in the art from the present disclosure.

In any aspect and/or embodiment, the Schulz-Flory K value can bedetermined using any one or more of the C₈, C₁₀, C₁₂, C₁₄, or C₁₆oligomer product. In an embodiment, the Schulz-Flory K value can be anaverage of any two or more Schulz-Flory K values using differentadjacent pairs of produced oligomers described herein. In someembodiments, the Schulz-Flory K value can be an average of any twoSchulz-Flory K values described herein; alternatively, any threeSchulz-Flory K values described herein; or alternatively, any fourSchulz-Flory K values described herein. For example, the Schulz-Flory Kvalue can be determined using the C₈ and C₁₀ oligomer product;alternatively, the C₁₀ and C₁₂ oligomer product; alternatively, the C₁₂and C₁₄ oligomer product; alternatively, the C₁₄ and C₁₆ oligomerproduct; alternatively, the C₈, C₁₀, and C₁₂ oligomer product, oralternatively, the C₁₀, C₁₂, and C₁₄ oligomer product, among othercombinations of oligomer product.

In any aspect and/or embodiment wherein hydrogen is utilized, theoligomer product can be formed at, the reaction zone can have, or thereaction zone can operate at, a minimum hydrogen partial pressure of 1psi (6.9 kPa), 2 psi (14 kPa); 5 psi (34 kPa), 10 psi (69 kPa), 15 psi(103 kPa), 20 psi (138 kPa), 30 psi (206 kPa); alternatively oradditionally, a maximum hydrogen partial pressure of 150 psi (1.03 MPa),100 psi (689 kPa), 75 psi (517 kPa), or 50 psi (345 kPa). In anembodiment, the oligomer product can be formed at, the reaction zone canhave, or the reaction zone can operate at, a hydrogen partial pressurein the range of any minimum hydrogen partial pressure disclosed hereinto any maximum hydrogen partial pressure disclosed herein. In somenon-limiting embodiments wherein hydrogen is utilized, the oligomerproduct can be formed at, the reaction zone can have, or the reactionzone can operate at, a hydrogen partial pressure in the range of 1 psi(6.9 kPa) to 150 psi (1.4 MPa), from 5 psi (34 kPa) to 100 psi (689kPa), from 10 psi (69 kPa) to 100 psi (689 kPa), or from 15 psi (100kPa) to 75 psi (517 kPa). Other hydrogen partial pressure ranges thatcan be utilized are readily apparent to those of ordinary skill in theart with the aid of this disclosure.

In any aspect and/or embodiment wherein hydrogen is utilized, theoligomer product can be formed at, the reaction zone can have, or thereaction zone can operate at, a minimum hydrogen to ethylene mass ratioof (0.05 g hydrogen)/(kg ethylene), (0.1 g hydrogen)/(kg ethylene),(0.25 g hydrogen)/(kg ethylene), (0.4 g hydrogen)/(kg ethylene), or (0.5g hydrogen)/(kg ethylene); alternatively or additionally, a maximumhydrogen to ethylene mass ratio can be (5 g hydrogen)/(kg ethylene), (3g hydrogen)/(kg ethylene), (2.5 g hydrogen)/(kg ethylene), (2 ghydrogen)/(kg ethylene), or (1.5 g hydrogen)/(kg ethylene). In anembodiment, the oligomer product can be formed at, the reaction zone canhave, or the reaction zone can operate at, a hydrogen to ethylene massratio in the range of any minimum hydrogen to ethylene mass ratiodisclosed herein to any maximum hydrogen to ethylene mass ratiodisclosed herein. In some non-limiting embodiments, the oligomer productcan be formed at, the reaction zone can have, or the reaction zone canoperate at, a hydrogen to ethylene mass ratio in the range of (0.05 ghydrogen)/(kg ethylene) to (5 g hydrogen)/(kg ethylene), from (0.25 ghydrogen)/(kg ethylene) to (5 g hydrogen)/(kg ethylene), from (0.25 ghydrogen)/(kg ethylene) to (4 g hydrogen)/(kg ethylene), from (0.4 ghydrogen)/(kg ethylene) to (3 g hydrogen)/(kg ethylene), from (0.4 ghydrogen)/(kg ethylene) to (2.5 g hydrogen)/(kg ethylene), from (0.4 ghydrogen)/(kg ethylene) to (2 g hydrogen)/(kg ethylene), or from (0.5 ghydrogen)/(kg ethylene) to (2 g hydrogen)/(kg ethylene). Other hydrogento ethylene mass ratio ranges that can be utilized are readily apparentto those of ordinary skill in the art with the aid of this disclosure.

Without being limited to theory, it is believed that the presence of thesecond metal salt in processes utilizing a heteroatomic ligand firstmetal salt complex can increase the stability of and/or can increase thelifetime of the active catalytic species produced by contacting theheteroatomic ligand first metal salt with the organoaluminum compound.In a particular aspect of the present disclosure, processes utilizingany second metal salt to the heteroatomic ligand of the heteroatomicligand metal salt complex (or second metal salt to the heteroatomicligand metal salt complex) can have a C₄-C₂₀ productivity at least 5%,10% 13%, 15%, or 17% greater than the C₄-C₂₀ productivity of anotherwise similar process wherein an equivalent molar ratio of thesecond metal salt to the heteroatomic ligand of the heteroatomic ligandmetal salt complex (or second metal salt to the heteroatomic ligandmetal salt complex) is less than 0.1:1. In a non-limiting aspect, theC₄-C₂₀ productivity for processes utilizing a second metal salt and aheteroatomic ligand first metal salt complex (or second metal salt tothe heteroatomic ligand metal salt complex) can be less than or equal to100%, 75%, 50%, or 40% the C₄-C₂₀ productivity of an otherwise similarprocess wherein an equivalent molar ratio of the second metal salt tothe heteroatomic ligand of the heteroatomic ligand metal salt complex(or second metal salt to the heteroatomic ligand metal salt complex) isless than 0.1:1. In some non-limiting embodiments, the C₄-C₂₀productivity increase can range from any minimum C₄-C₂₀ productivityincrease disclosed herein to any maximum C₄-C₂₀ productivity increasedisclosed herein. In a non-limiting embodiment, the C₄-C₂₀ productivitycan be in the range of 5% to 100%, 10% to 100%, 10% to 75%, 13% to 50%,13% to 50%, 15% to 40%, or 17% to 40% greater than the C₄-C₂₀productivity of an otherwise similar process wherein an equivalent molarratio of the second metal salt to the heteroatomic ligand of theheteroatomic ligand metal salt complex (or second metal salt to theheteroatomic ligand metal salt complex) is less than 0.1:1. Other C₄-C₂₀productivity increase ranges are readily apparent to those skilled inthe art with the aid of this disclosure. Equivalent molar ratios of thesecond metal salt to the heteroatomic ligand of the heteroatomic ligandmetal salt complex (or second metal salt to the heteroatomic ligandmetal salt complex) for the processes described herein are independentlydescribed herein and these independently described equivalent molarratio of the second metal salt to the heteroatomic ligand of theheteroatomic ligand metal salt complex (or second metal salt to theheteroatomic ligand metal salt complex) can be utilized withoutlimitation to further describe the C₄-C₂₀ productivity increases whencompared to an otherwise similar process wherein an equivalent molarratio of the second metal salt to the heteroatomic ligand of theheteroatomic ligand metal salt complex (or second metal salt to theheteroatomic ligand metal salt complex) is less than 0.1:1.

Without being limited to theory, it is believed that in processesutilizing a metal salt and a heteroatomic ligand, an equivalent molarratio of metal salt to heteroatomic greater than the 1:1 ratio toproduce the heteroatomic ligand metal salt complex can increase thestability of and/or can increase the lifetime of the active catalyticspecies produced by contacting the metal salt, heteroatomic ligand, andorganoaluminum compound. In a particular aspect of the presentdisclosure, processes utilizing a equivalent molar ratio of metal saltto heteroatomic ligand greater than the 1:1 equivalent molar rationeeded to produce the heteroatomic ligand metal salt complex (anyequivalent molar ratio of metal salt to heteroatomic disclosed herein)can have a C₄-C₂₀ productivity at least 100%, 200% 300%, 400%, or 500%greater than the C₄-C₂₀ productivity of an otherwise similar processwherein an equivalent molar ratio of the metal salt to the heteroatomicligand is less than 1.1:1. In a non-limiting aspect, the C₄-C₂₀productivity for processes utilizing a metal salt and a heteroatomicligand can be less than or equal to 10,000%, 5,000%, 3,000%, or 1,000%the C₄-C₂₀ productivity of an otherwise similar process wherein anequivalent molar ratio of the metal salt to the heteroatomic ligand isless than 1.1:1. In some non-limiting embodiments, the C₄-C₂₀productivity increase can range from any minimum C₄-C₂₀ productivityincrease disclosed herein to any maximum C₄-C₂₀ productivity increasedisclosed herein. In a non-limiting embodiment, the C₄-C₂₀ productivitycan be in the range of 100% to 10,000%, 200% to 5,000%, 300% to 3,000%,400% to 3,000%, 500% to 3,000%, 300% to 1,000%, 400% to 1,000%, or 500%to 1,000% of the C₄-C₂₀ productivity of an otherwise similar processwherein an equivalent molar ratio of the metal salt to the heteroatomicligand is less than 1.1:1. Other C₄-C₂₀ productivity increase ranges arereadily apparent to those skilled in the art with the aid of thisdisclosure. Equivalent molar ratios of metal salt to heteroatomic ligandfor the processes described herein are independently described hereinand these independently described equivalent molar ratio of metal saltto heteroatomic ligand can be utilized without limitation to furtherdescribe the C₄-C₂₀ productivity increases when compared to an otherwisesimilar process wherein an equivalent molar ratio of the metal salt tothe heteroatomic ligand is less than 1.1:1.

In any aspect and/or embodiment, the processes described herein canproduce an oligomer product with high selectivity to linear alphaolefins; or alternatively, to normal alpha olefins. In some embodiments,the processes described herein can produce a reactor effluent whereinthe C₆ olefin oligomer product has a 1-hexene content of at least 98.5wt. %; alternatively, at least 98.75 wt. %; alternatively, at least 99.0wt. %; or alternatively, at least 99.25 wt. %. In other embodiments, theprocesses described herein can produce a reactor effluent wherein the C₈olefin oligomer product has a 1-octene content of at least 98 wt. %;alternatively, at least 98.25 wt. %; alternatively, at least 98.5 wt. %;alternatively, at least 98.75 wt. %; or alternatively, at least 99.0 wt.%. In yet other embodiments, the processes described herein can producea reactor effluent wherein the C₁₀ olefin oligomer product has a1-decene content of at least 97.5 wt. %; alternatively, at least 97.75wt. %; alternatively, at least 98 wt. %; alternatively, at least 98.25wt. %; or alternatively, at least 98.5 wt. %. In yet other embodiments,the processes described herein can produce a reactor effluent whereinthe C₁₂ olefin oligomer product has a 1-dodecene content of at least96.5 wt. %; alternatively, at least 97 wt. %; alternatively, at least97.5 wt. %; alternatively, at least 97.75 wt. %; or alternatively, atleast 98.0 wt. %. In yet other embodiments, the processes describedherein can produce a reactor effluent wherein the oligomer product cancomprise any combination of any C₆ olefin oligomer product 1-hexenecontent described herein, any Ca olefin oligomer product 1-octenecontent described herein, any C₁₀ olefin oligomer product 1-decenecontent described herein, and/or any C₁₂ olefin oligomer product1-dodecne content described herein. In some non-limiting examples, theprocesses described herein can produce a reactor effluent having a C₆olefin oligomer product 1-hexene content of at least 99 wt. % and a C₁₂olefin oligomer product 1-dodecene content of at least 97.5 wt. %;alternatively, a C₈ olefin oligomer product 1-octene content of at least98.5 wt. % and a C₁₂ olefin oligomer product 1-dodecene octene contentof at least 97.5 wt. %; or alternatively, a C₆ olefin oligomer product1-hexene content of at least 99 wt. %, a C₈ olefin oligomer product1-octene content of at least 98.5 wt. %, a C₁₀ olefin oligomer product1-decene content of at least 98 wt. %, and a C₁₂ olefin oligomer product1-dodecene content of at least 97.5 wt. %. Other combinations of reactoreffluent olefin oligomer 1-alkene contents are readily apparent from thepresent disclosure.

Various aspects and/or embodiments described herein can refer tosubstituted groups or compounds. In an embodiment, each substituent ofany aspect and/or embodiment calling for a substituent can be a halogen,a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogenor a hydrocarbyl group; alternatively, a halogen or a hydrocarboxygroup; alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. In an embodiment, each hydrocarbylgroup or substituent of any aspect and/or embodiment calling for asubstituent can be a C₁ to C₁₀, or a C₁ to C₅ hydrocarbyl group. In anembodiment, each hydrocarboxy group or substituent of any aspect and/orembodiment calling for a substituent can be a C₁ to C₁₀, or a C₁ to C₅hydrocarboxy group. In an embodiment, any halide substituent of anyaspect and/or embodiment calling for a halide substituent can be afluoride, chloride, bromide, or iodide; alternatively, a fluoride orchloride. In some embodiments, any halide substituent of any aspectand/or embodiment calling for a substituent can be a fluoride;alternatively, a chloride; alternatively, a bromide; or alternatively,an iodide.

In an embodiment, any hydrocarbyl group or substituent of any aspectand/or embodiment calling for a substituent can be an alkyl group, anaryl group, or an aralkyl group; alternatively, an alkyl group;alternatively, an aryl group; or alternatively, an aralkyl group. In anembodiment, any alkyl group of any aspect and/or embodiment calling fora substituent can be a methyl group, an ethyl group, an n-propyl group,an isopropyl group, an n-butyl group, a sec-butyl group, an isobutylgroup, a tert-butyl group, an n-pentyl group, a 2-pentyl group, a3-pentyl group, a 2-methyl-1-butyl group, a tert-pentyl group, a3-methyl-1-butyl group, a 3-methyl-2-butyl group, or a neo-pentyl group;alternatively, a methyl group, an ethyl group, an isopropyl group, atert-butyl group, or a neo-pentyl group; alternatively, a methyl group;alternatively, an ethyl group; alternatively, an isopropyl group;alternatively, a tert-butyl group; or alternatively, a neo-pentyl group.In an embodiment, any aryl group of any aspect and/or embodiment callingfor a substituent can be phenyl group, a tolyl group, a xylyl group, ora 2,4,6-trimethylphenyl group; alternatively, a phenyl group;alternatively, a tolyl group, alternatively, a xylyl group; oralternatively, a 2,4,6-trimethylphenyl group. In an embodiment, anyaralkyl group of any aspect and/or aspect calling for a substituent canbe benzyl group or an ethylphenyl group (2-phenyleth-1-yl or1-phenyleth-1-yl); alternatively, a benzyl group; alternatively, anethylphenyl group; alternatively, a 2-phenyleth-1-yl group; oralternatively, a 1-phenyleth-1-yl group.

In an embodiment, any hydrocarboxy group or substituent of any aspectand/or embodiment calling for a substituent can be an alkoxy group, anaryloxy group, or an aralkoxy group; alternatively, an alkoxy group;alternatively, an aryloxy group; or alternatively, an aralkoxy group. Inan embodiment, any alkoxy group of any aspect and/or embodiment callingfor a substituent can be a methoxy group, an ethoxy group, an n-propoxygroup, an isopropoxy group, an n-butoxy group, a sec-butoxy group, anisobutoxy group, a tert-butoxy group, an n-pentoxy group, a 2-pentoxygroup, a 3-pentoxy group, a 2-methyl-1-butoxy group, a tert-pentoxygroup, a 3-methyl-1-butoxy group, a 3-methyl-2-butoxy group, or aneo-pentoxy group; alternatively, a methoxy group, an ethoxy group, anisopropoxy group, a tert-butoxy group, or a neo-pentoxy group;alternatively, a methoxy group; alternatively, an ethoxy group;alternatively, an isopropoxy group; alternatively, a tert-butoxy group;or alternatively, a neo-pentoxy group. In an embodiment, any aryloxygroup of any aspect and/or embodiment calling for a substituent can bephenoxy group, a toloxy group, a xyloxy group, or a2,4,6-trimethylphenoxy group; alternatively, a phenoxy group;alternatively, a toloxy group, alternatively, a xyloxy group; oralternatively, a 2,4,6-trimethylphenoxy group. In an aspect, anyaralkoxy group of any aspect or aspect calling for a substituent can bea benzoxy group.

For the purpose of any U.S. national stage filing from this application,all publications and patents mentioned in this disclosure areincorporated herein by reference in their entireties, for the purpose ofdescribing and disclosing the constructs and methodologies described inthose publications, which might be used in connection with the methodsof this disclosure. Any publications and patents discussed above andthroughout the text are provided solely for their disclosure prior tothe filing date of the present application. Nothing herein is to beconstrued as an admission that the applicants are not entitled toantedate such disclosure by virtue of prior disclosure.

In any application before the United States Patent and Trademark Office,the Abstract of this application is provided for the purpose ofsatisfying the requirements of 37 C.F.R. § 1.72 and the purpose statedin 37 C.F.R. § 1.72(b) “to enable the United States Patent and TrademarkOffice and the public generally to determine quickly from a cursoryinspection the nature and gist of the technical disclosure.” Therefore,the Abstract of this application is not intended to be used to construethe scope of the claims or to limit the scope of the subject matter thatis disclosed herein. Moreover, any headings that can be employed hereinare also not intended to be used to construe the scope of the claims orto limit the scope of the subject matter that is disclosed herein. Anyuse of the past tense to describe an example otherwise indicated asconstructive or prophetic is not intended to reflect that theconstructive or prophetic example has actually been carried out.

The present disclosure is further illustrated by the examples, which arenot to be construed in any way as imposing limitations upon the scopethereof. On the contrary, it is to be clearly understood that resort canbe had to various other aspects, embodiments, modifications, andequivalents thereof which, after reading the description herein, cansuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present disclosure or the scope of the appendedclaims.

The data and descriptions provided in the examples are given to showparticular aspects and/or embodiments of the compounds, catalystsystems, and olefin oligomerization and/or olefin polymerization methodsdisclosed, and to demonstrate a number of the practices and advantagesthereof. The examples are given as a more detailed demonstration of someof the aspects and/or embodiments described herein and are not intendedto limit the disclosure or claims in any manner.

ADDITIONAL DISCLOSURE

The following enumerated embodiments of the present disclosures areprovided as non-limiting examples.

Embodiment 1

A process for forming an oligomer product comprising: a) introducinginto a reaction zone i. ethylene; ii. a heteroatomic ligand metal saltcomplex comprising a heteroatomic ligand complexed to a first metal saltwhere the first metal salt is an iron salt, a cobalt salt, or acombination thereof; iii. a second metal salt wherein an equivalentmolar ratio of the second metal salt to the heteroatomic ligand of theheteroatomic ligand metal salt complex (or second metal salt to theheteroatomic ligand metal salt complex) is at least 0.5:1 (or any otherequivalent molar ratio of the second metal salt to the heteroatomicligand of the heteroatomic ligand metal salt complex, or second metalsalt to the heteroatomic ligand metal salt complex, disclosed herein)and where the second metal salt is an iron salt, a cobalt salt, or anycombination thereof; iv. an organoaluminum compound; v. optionallyhydrogen; and vi. optionally an organic reaction medium; and b) formingan oligomer product in the reaction zone.

Embodiment 2

The process of embodiment 1, wherein the equivalent molar ratio of thesecond metal salt to the heteroatomic ligand of the heteroatomic ligandmetal salt complex (or second metal salt to the heteroatomic ligandmetal salt complex) ranges from 1.2:1 to 50:1 (or any other equivalentmolar ratio of the second metal salt to the heteroatomic ligand of theheteroatomic ligand metal salt complex, or second metal salt to theheteroatomic ligand metal salt complex, disclosed herein).

Embodiment 3

The process of embodiment 1 or 2, wherein a C₄-C₂₀ productivity is atleast 10% greater than the C₄-C₂₀ productivity of an otherwise similarprocess wherein an equivalent molar ratio of the second metal salt tothe heteroatomic ligand of the heteroatomic ligand metal salt complex(or second metal salt to the heteroatomic ligand metal salt complex) isless than 0.1:1.

Embodiment 4

The process of any one of embodiments 1 to 3, where the first metal saltcomprises an iron halide, an iron β-diketonate, an iron carboxylate, orany combination thereof and the second metal salt comprises an ironhalide, an iron β-diketonate, an iron carboxylate, or any combinationthereof.

Embodiment 5

The process of any one of embodiments 1 to 4, where the first metal saltand the second metal salt are the same or different.

Embodiment 6

A process for forming an oligomer product comprising: a) introducinginto a reaction zone i. ethylene; ii. a heteroatomic ligand; iii. ametal salt where 1) the metal salt is an iron salt, a cobalt salt, orany combination thereof, and 2) an equivalent molar ratio of the metalsalt to the heteroatomic ligand is at least 1.5:1 (or any otherequivalent molar ratio of the metal salt to the heteroatomic liganddisclosed herein); iv. an organoaluminum compound; v. optionallyhydrogen; and vi. optionally an organic reaction medium; and b) formingan oligomer product in the reaction zone.

Embodiment 7

The process of embodiment 6, wherein the equivalent molar ratio of themetal salt to the heteroatomic ligand ranges from 1.5:1 to 50:1 (or anyother equivalent molar ratio of the metal salt to the heteroatomicligand disclosed herein).

Embodiment 8

The process of embodiment 6 or 7, wherein a C₄-C₂₀ productivity is atleast 100% greater than the C₄-C₂₀ productivity of an otherwise sameprocess wherein an equivalent molar ratio of the metal salt to theheteroatomic ligand is less than 1.1:1.

Embodiment 9

The process of any one of embodiments 6 to 8, where the metal saltcomprises an iron halide, an iron β-diketonate, an iron carboxylate, orany combination thereof.

Embodiment 10

The process of any one of embodiments 1 to 9, wherein the heteroatomicligand or the heteroatomic ligand of the heteroatomic ligand metal saltcomplex comprises 1) a bidentate metal salt complexing moiety, or 2) atridentate metal salt complexing moiety, wherein the bidentate metalsalt complexing moiety and the tridentate metal salt complexing moietyeach independently comprise at least two metal salt complexing groupsselected from the group consisting of an imine group and an aromaticnitrogen atom containing group.

Embodiment 11

The process of any one of embodiments 1 to 10, wherein the heteroatomicligand or the heteroatomic ligand of the metal salt complex comprises anα-diimine, a pyridine bisimine, a phenanthroline imine, or anycombination thereof.

Embodiment 12

The process of embodiment 11, wherein the heteroatomic ligand or theheteroatomic ligand of the metal salt complex is the α-diimine and theα-diimine comprises i) an α-diimine group, ii) a first imine groupconsisting of a hydrocarbyl group or substituted hydrocarbyl groupattached to a first imine nitrogen atom of the α-diimine group, and iii)a second imine group comprising a first metal salt complexing group anda linking group linking the first metal salt complexing group to asecond imine nitrogen atom of the α-diimine group.

Embodiment 13

The process of embodiment 11, wherein the α-diimine comprises i) anα-diimine group derived from an aromatic diacyl compound, ii) a firstimine group consisting of an aryl group or substituted aryl group, andiii) a second imine group comprising a diarylphosphinyl first metal saltcomplexing group and a —CH₂CH₂— linking group linking thediarylphosphinyl first metal salt complexing group to the second iminenitrogen atom.

Embodiment 14

The process of embodiment 11, wherein the α-diimine comprises i) anα-diimine group derived from acenaphthenequinone, phenanthrenequinone,or pyrenequinone, ii) a first imine group consisting of an2,6-dihydrocarbylphenyl group, and iii) a second imine group comprisinga diphenylphosphinyl first metal salt complexing group or adi(substituted phenyl)phosphinyl first metal complexing group and a—CH₂CH₂— linking group linking the first metal salt complexing group tothe second imine nitrogen atom.

Embodiment 15

The process of any one of embodiments 1 to 14 wherein the heteroatomicligand metal salt complex has a structure selected from the groupconsisting of ADIFe I, ADIFe II, ADIFe III, ADIFe IV, ADIFe V, ADIFe VI,ADIFe VII, ADIFe VIII, ADIFe IX, ADIFe X, ADIFe XII, ADIFe XIII, andADIFe XIV.

Embodiment 16

The process of embodiment 11, wherein the heteroatomic ligand or theheteroatomic ligand of the heteroatomic ligand metal salt complex is thepyridine bisimine and the pyridine bisimine comprises i) a2,6-bis[(arylimine)hydrocarbyl]pyridine wherein the aryl groups can bethe same or different, ii) a bis[(substitutedarylimine)hydrocarbyl]pyridine wherein the substituted aryl groups canbe the same or different, or iii) an[(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridine,or iii) an [(arylimine)hydrocarbyl],[(substitutedarylimine)hydrocarbyl]-pyridine.

Embodiment 17

The process of embodiment 16, wherein the pyridine bisimine has 1) one,two, or three of the aryl groups and/or substituted aryl groupspositions ortho to the carbon atom attached to the imine nitrogenindependently are a halogen, a primary carbon atom group, or a secondarycarbon atom group and the remainder of the aryl groups and/orsubstituted aryl groups positions ortho to the carbon atom attached tothe imine nitrogen are hydrogen, 2) one of the aryl groups and/orsubstituted aryl groups positions ortho to the carbon atom attached tothe imine nitrogen is a tertiary carbon atom group, none, one, or two ofthe aryl groups and/or substituted aryl groups positions ortho to thecarbon atom attached to the imine nitrogen independently are a halogen,a primary carbon atom group or a secondary carbon atom group, and theremainder of the aryl groups and/or substituted aryl groups positionsortho to the carbon atom attached to the imine nitrogen are hydrogen, 3)two of the aryl groups and/or substituted aryl groups positions ortho tothe carbon atom attached to the imine nitrogen independently are atertiary carbon atom group, none, or one of the aryl groups and/orsubstituted aryl groups positions ortho to the carbon atom attached tothe imine nitrogen independently are a halogen, a primary carbon atomgroup, or a secondary carbon atom group, and the remainder of the arylgroups and/or substituted aryl groups positions ortho to the carbon atomattached to the imine nitrogen are hydrogen, 4) one or two of the arylgroups and/or substituted aryl groups positions ortho to the carbon atomattached to the imine nitrogen independently are a tertiary carbon atomgroup(s) and the remainder of the aryl groups and/or substituted arylgroups positions ortho to the carbon atom attached to the imine nitrogenare hydrogen, 5) one or two of the aryl groups and/or substituted arylgroups positions ortho to the carbon atom attached to the imine nitrogenare a quaternary carbon atom group and the remainder of the aryl groupsand/or substituted aryl groups positions ortho to the carbon atomattached to the imine nitrogen are hydrogen, or 6) all four of thesubstituted aryl groups positions ortho to the carbon atom attached tothe imine nitrogen are fluorine.

Embodiment 18

The process of embodiment 16, wherein the pyridine bisimine is selectedfrom the group consisting of 2,6-bis[(phenylimine) methyl]pyridine,2,6-bis[(2-methylphenylimine)methyl]pyridine,2,6-bis[(2-ethylphenylimine)methyl]pyridine,2,6-bis[(2-isopropylphenylimine)methyl]pyridine,2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine,2,6-bis[(2,6-diethylphenylimine)methyl]pyridine,2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)-methyl]pyridine,2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridine,and2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridine.

Embodiment 19

The process of embodiment 11, wherein the heteroatomic ligand or theheteroatomic ligand of the heteroatomic ligand metal salt complex is thephenanthroline imine and the phenanthroline imine comprises a2-(hydrocarbylimine)-1,10-phenanthroline, a2-[(hydrocarbylimine)hydrocarbyl]-1,10-phenanthroline, a2-(arylimine)-1,10-phenanthroline, a2-[(arylimine)hydrocarbyl]-1,10-phenanthroline, a 2-(substitutedarylimine)-1,10-phenanthroline, or a 2-[(substitutedarylimine)hydrocarbyl]-1,10-phenanthroline.

Embodiment 20

The process of embodiment 19, wherein the phenanthroline imine comprisesa 2-(2,6-dialkylphenylimine)-1,10-phenanthroline, a2-[(2,6-dialkylphenylimine)alkyl]-1,10-phenanthroline, a2-[(2,6-dialkylphenylimine)phenyl]-1,10-phenanthroline, a2-(2,4,6-trialkylphenylimine)-1,10-phenanthroline, a2-[(2,4,6-trialkylphenylimine)alkyl]-1,10-phenanthroline, a2-[(2,4,6-trialkylphenylimine)phenyl]-1,10-phenanthroline, a2-(2,6-dihalophenylimine)-1,10-phenanthroline, a2-[(2,6-dihalophenylimine)alkyl]-1,10-phenanthroline, and a2-[(2,6-dihalophenylimine)phenyl]-1,10-phenanthroline, or anycombination thereof.

Embodiment 21

The process of embodiment 19, wherein phenanthroline imine is selectedfrom the group consisting of2-(2,6-difluorophenylimine)-1,10-phenanthroline,2-(2,6-dichlorophenylimine)-1,10-phenanthroline,2-(2,6-dibromophenylimine)-1,10-phenanthroline,2-(2,6-dimethylphenylimine)-1,10-phenanthroline,2-(2,6-diethylphenylimine)-1,10-phenanthroline,2-(2,6-diisopropylphenylimine)-1,10-phenanthroline,2-[(2,6-difluorophenylimine)methyl]-1,10-phenanthroline,2-[(2,6-dichlorophenylimine)methyl]-1,10-phenanthroline,2-[(2,6-dibromophenylimine)methyl]-1,10-phenanthroline,2-[(2,6-dimethylphenylimine)methyl]-1,10-phenanthroline,2-[(2,6-diethylphenyl-imine)methyl]-1,10-phenanthroline,2-[(2,6-diisopropylphenylimine)methyl]-1,10-phenanthroline,2-[(2,6-diethylphenylimine)ethyl]-1,10-phenanthroline,2-[(2,6-diethylphenylimine)-n-propyl]-1,10-phenanthroline,2-[(2,6-diethylphenylimine)iso-propyl]-1,10-phenanthroline,2-[(2,4,6-tribromophenylimine)-methyl]-1,10-phenanthroline,2-[(2,4,6-trimethylphenylimine)methyl]-1,10-phenanthroline,2-[(2,6-dimethyl-4-bromophenylimine)methyl]-1,10-phenanthroline,2-[(2,6-dibromo-4-methylphenylimine)-methyl]-1,10-phenanthroline,2-[(2,6-dibromo-4-chlorophenylimine)methyl]-1,10-phenanthroline,2-[(2,6-dimethylphenylimine)phenyl]-1,10-phenanthroline,2-[(2,6-diethylphenylimine)phenyl]-1,10-phenanthroline, and2-[(2,6-diisopropylphenylimine)phenyl]-1,10-phenanthroline.

Embodiment 22

The process of any one of embodiments 1 to 21, wherein theorganoaluminum compound comprises an aluminoxane.

Embodiment 23

The process of embodiment 22, wherein the aluminoxane comprisesmethylaluminoxane, a modified methylaluminoxane, ethylaluminoxane,n-propylaluminoxane, iso-propylaluminoxane, n-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane,1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane,iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof.

Embodiment 24

The process of any one of embodiments 1 to 23, wherein the organo groupsof the organoaluminum compound are substantially devoid of β,γ-branchedorgano groups and/or β,δ-branched organo groups.

Embodiment 25

The process of any one of embodiments 1 to 24, wherein the oligomerproduct is formed under conditions having (or the reaction zone has) anheteroatomic ligand molar equivalent concentration or heteroatomicligand metal salt complex molar equivalent concentration of at least1×10⁻⁶ mmol/kg (or any other heteroatomic ligand molar equivalentconcentration or heteroatomic ligand metal salt complex molar equivalentconcentration disclosed herein).

Embodiment 26

The process of any one of embodiments 1 to 25, wherein the oligomerproduct is formed under conditions having (or the reaction zone has) analuminum of the organo aluminum compound to heteroatomic ligand molarequivalent ratio or aluminum to heteroatomic ligand metal salt complexmolar equivalent ratio of at least 100:1 (or any other aluminum toheteroatomic ligand molar equivalent ratio or aluminum to heteroatomicligand metal salt complex molar equivalent ratio disclosed herein).

Embodiment 27

The process of any one of embodiments 1 to 26, wherein the oligomerproduct is formed under conditions having (or the reaction zone has) analuminum of the organoaluminum compound concentration of at least 0.3mmol Al/kg (or any other aluminum of the organoaluminum compoundconcentration disclosed herein).

Embodiment 28

The process of any one of embodiments 1 to 27, wherein the oligomerproduct is formed under conditions having (or the reaction zone has) anethylene partial pressure of at least 100 psi (or any other ethylenepartial pressure disclosed herein.

Embodiment 29

The process of any one of embodiments 1 to 28, wherein the oligomerproduct is formed under conditions having (or the reaction zone has) atemperature of at least 0° C. (or any other temperature disclosedherein).

Embodiment 30

The process of any one of embodiments 1 to 29, wherein the processutilizes a hydrogen and the oligomer product is formed under conditionshaving (or the reaction zone has) a hydrogen partial pressure of atleast 5 psi (or any other hydrogen partial pressure disclosed herein).

Embodiment 31

The process of any one of embodiments 1 to 30, wherein the processutilizes a hydrogen and the oligomer product is formed under conditionshaving (or the reaction zone has) a hydrogen to ethylene mass ratio ofat least (0.05 g hydrogen)/(kg ethylene) (or any other hydrogen toethylene mass ratio disclosed herein).

Embodiment 32

The process of any one of embodiments 1 to 31, wherein the processutilizes an organic reaction medium and the organic reaction mediumcomprises, or consists essentially of, one or more aliphatichydrocarbons.

Embodiment 33

The process of embodiments 32, wherein the organic reaction mediumcomprises, or consists essentially of, one or more C₈ to C₁₈ aliphatichydrocarbons.

Embodiment 34

The process of embodiments 32, wherein the organic reaction mediumcomprises, or consists essentially of, one or more C₈ to C₁₆ saturatedaliphatic hydrocarbons.

Embodiment 35

The process of embodiments 32, wherein the organic reaction mediumcomprises, or consists essentially of, one or more C₈ to C₁₆ olefinicaliphatic hydrocarbons.

Embodiment 36

The process of embodiments 32, wherein the organic reaction mediumcomprises, or consists essentially of, 1-decene, 1-dodecene,1-tetradecene, or any combination thereof.

Embodiment 37

The process of any one of embodiments 32 to 36, wherein the organicreaction medium is substantially devoid of a halogenated compound.

Embodiment 38

The process of any one of embodiments 32 to 37, wherein the oligomerproduct is formed under conditions having (or the reaction zone has) anethylene to organic reaction medium mass ratio of at least 0.8:1 (or anyother ethylene to organic reaction medium mass ratio disclosed herein).

Embodiment 39

The process of any one of embodiments 1 to 38, wherein the oligomerproduct has a Schultz-Flory K value in the range of 0.4 to 0.9 (or anyother Schultz-Flory K value disclosed herein).

EXAMPLES

All operations were performed in an oxygen free and moisture freeenvironment. Solvents were dried over 13× molecular sieves, and ethylenewas purified using in-stream de-oxygenation and moisture removal beds.MMAO-3A was purchased from Akzo Nobel and utilized as received.

Heteroatomic metal salt complex ADIFe XIV was prepared using methodsdisclosed in US 2007/00221608 A1. Heteroatomic ligand PBI 1 was preparedusing methods disclosed in US 2002/0016425 A1.

Examples 1-6

Ethylene oligomerization runs using no additional metal salt andadditional metal salt, Fe(acac)₂, were run in pairs on the same dayutilizing the same reactor to allow for comparison between the ethyleneoligomerization runs performed on the same day. In a nitrogen-filleddrybox, a stock toluene solution of 2.0 mg/mL (2.53×10⁻³ meq/mL) ofADIFe XIV and a stock toluene solution of 4.0 mg/mL (1.57×10⁻² meq/mL)of Fe(acac)₂ were prepared. The appropriate amount of the ADIFe XIV andthe Fe(acac)₂ stock solutions were added to a 5 mL NMR tube to providethe desired quantity of ADIFe XIV and of Fe(acac)₂ for the ethyleneoligomerization. The NMR tube was then sealed. Also in thenitrogen-filled drybox, a glass charger was charged with 200 mLcyclohexane, approximately 1.0 g of n-nonane internal standard, and theappropriate amount of MMAO-7 (Akzo Nobel, 7.0 wt % Al) to achieve thedesired α-diimine ligand to aluminum molar ratio for the ethyleneoligomerization. The glass charger was then sealed. The NMR tube andcharger were removed from the drybox. The NMR tube was secured to thestirrer shaft of a 1000 mL autoclave reactor with wire in a manner wherethe glass would shatter on starting the mixer. The autoclave reactor wasthen sealed and evacuated under high vacuum. The glass charger was thenaffixed to a charging port on the top of the autoclave reactor. Afterevacuating the reactor for several minutes, the entire contents of theglass charger were loaded into the autoclave reactor under vacuum. Theautoclave reactor was then degassed with ethylene by carrying outseveral fill/vent cycles. The reactor was then pressurized with ethyleneto 400 psig (2.8 MPa). Stirring was initiated resulting in breakage ofthe 5 mm NMR tube and activation of the catalyst. Ethylene was then fedto the autoclave reactor on demand to maintain a pressure of 400 psig(2.8 MPa) for the remainder of the reaction. The reaction temperaturewas maintained at a temperature of 50 to 60° C. by way of cooling waterpassed through internal cooling coils inside the autoclave reactor.After 15 min, the reactor was cooled to room temperature and vented toatmospheric pressure. The liquid products were analyzed by a gaschromatograph with a flame ionization detector (FID) detector againstthe n-nonane internal standard. Table 1 details the results of theseethylene oligomerization examples. Ethylene oligomerization examples 1and 2 were run on the same day, while ethylene oligomerization examples3 and 4 were run on a different day, and ethylene oligomerizationexamples 5 and 6 were run on yet a different day.

TABLE 1 Productivity C₁₂/C₁₀ mass of Al:ADIFe Fe(acac)₂:ADIFe g(C₄-C₂₀)/ Schulz- ADIFe XIV, XIV, XIV Temp., grams mmol ADIFe Flory KExample mg Molar Ratio Molar Ratio ° C. (C₄-C₂₀) XIV value 1 0.75 1000 —50-60 15.45 17000 0.54 2 0.75 1000 10:1 50-60 19.09 21000 0.56 3 0.751000 — 50-60 15.66 17200 0.53 4 0.75 1000 10:1 50-60 16.74 18400 0.55 50.75 1000 — 50-60 18.02 19800 0.55 6 0.75 1000 10:1 50-60 23.76 261000.56

The results of Examples 1-6 demonstrate that the addition of a metalsalt to the ethylene oligomerization utilizing a heteroatomic ligandmetal salt complex increases the productivity of ethyleneoligomerization.

Examples 7-10

In a nitrogen-filled drybox, a stock cyclohexane solution of 0.14 mg/mL(3.68×10⁻⁴ meq/mL) of PBI 1 and a stock cyclohexane solution of 1.0mg/mL (3.94×10⁻³ meq/mL) of Fe(acac)₂ were prepared. The appropriateamount of the PBI 1 and of the Fe(acac)₂ stock solutions were added to a5 mL NMR tube to provide the desired quantity of PBI 1 and of Fe(acac)₂for the ethylene oligomerization. The NMR tube was then sealed. Also inthe nitrogen-filled drybox, a glass charger was charged with 200 mLcyclohexane, approximately 1.0 g of n-nonane internal standard, and theappropriate amount of MMAO-3A (Akzo Nobel, 7.0 wt % Al) to achieve thedesired PBI 1 to aluminum molar ratio for the ethylene oligomerization.The glass charger was then sealed. The NMR tube and charger were removedfrom the drybox. The NMR tube was secured to the stirrer shaft of a 1000mL autoclave reactor with wire in a manner where the glass would shatteron starting the mixer. The autoclave reactor was then sealed andevacuated under high vacuum. The glass charger was then affixed to acharging port on the top of the autoclave reactor. After evacuating thereactor for several minutes, the entire contents of the glass chargerwere loaded into the autoclave reactor under vacuum. The autoclavereactor was then degassed with ethylene by carrying out severalfill/vent cycles. The reactor was then pressurized with ethylene to 400psig (2.8 mPa). Stirring was initiated resulting in breakage of the 5 mmNMR tube and activation of the catalyst. Ethylene was then fed to theautoclave reactor on demand to maintain a pressure of 400 psig (2.8 mPa)for the remainder of the reaction. The reaction temperature wasmaintained at a temperature of 60 to 70° C. by way of cooling waterpassed through internal cooling coils inside the autoclave reactor.After 15 min, the reactor was cooled to room temperature and vented toatmospheric pressure. The liquid products were analyzed by a gaschromatograph with a flame ionization detector (FID) detector againstthe n-nonane internal standard. Table 2 details the results of theseethylene oligomerization examples.

TABLE 2 Productivity C₁₂/C₁₀ mass of PBI 1, Fe:PBI 1, Al:PBI 1, Temp.,grams g (C₄-C₂₀)/ Schulz-Flory Example mg Molar Ratio Molar Ratio ° C.(C₄-C₂₀) mmol PBI 1 K value 7 0.05  1:1 10,000 60-70  5.30  39,100 0.748 0.05  5:1 10,000 60-70 35.52 262,100 0.69 9 0.05 10:1 10,000 60-7045.22 333,700 0.73 10  0.05 20:1 10,000 60-70 31.65 233,600 0.71

The results of Examples 7-10 demonstrate that the use of a metal salt toheteroatomic ligand equivalent molar ratio greater than 1.2:1 in anethylene oligomerization utilizing a heteroatomic ligand and a metalsalt increases the productivity of ethylene oligomerization.

Examples 11-12

The heteroatomic ligand iron dichloride2-[(2,6-diethylphenylimine)methyl-1,10-phenanthroline iron dichloride(PhenIFe 1) is prepared using the procedures disclosed in CN 104418690A.

In a nitrogen-filled drybox, a stock toluene solution of 1.0 mg/mL(4.15×10⁻³ meq/mL) of PhenIFe 1 and a stock toluene solution 4.0 mg/mL(1.57×10⁻² meq/mL) of Fe(acac)₂ are prepared. The appropriate amount ofthe PhenIFe 1 and of the Fe(acac)₂ stock solutions are added to a 5 mLNMR tube to provide the desired quantity of PhenIFe 1 and of Fe(acac)₂for the ethylene oligomerization. The NMR tube is then sealed. Also inthe nitrogen-filled drybox, a glass charger is charged with 100 mLcyclohexane, approximately 1.0 g of n-nonane internal standard, and theappropriate amount of MMAO-7 (Akzo Nobel, 7.0 wt % Al) to achieve thedesired α-diimine ligand to aluminum molar ratio for the ethyleneoligomerization. The glass charger is then sealed. The NMR tube andglass charger are then removed from the drybox. The NMR tube is securedto the stirrer shaft of a 500 mL autoclave reactor with wire in a mannerwhere the glass will shatter on starting the mixer. The autoclavereactor is then sealed and evacuated under high vacuum. The glasscharger is then affixed to a charging port on the top of the autoclavereactor. After evacuating the reactor for several minutes, the entirecontents of the glass charger is loaded into the autoclave reactor undervacuum. The autoclave reactor is then degassed with ethylene by carryingout several fill/vent cycles. The reactor is then pressurized withethylene to 400 psig (2.8 MPa). Stirring is initiated resulting inbreakage of the 5 mm NMR tube and activation of the catalyst. Ethyleneis then fed to the autoclave reactor on demand to maintain a pressure of400 psig (2.8 MPa) for the remainder of the reaction. The reactiontemperature is maintained at a temperature of 60 to 70° C. by way ofcooling water passed through internal cooling coils inside the autoclavereactor. After 15 min, the reactor is cooled to room temperature andvented to atmospheric pressure. The liquid products are analyzed by agas chromatograph with a flame ionization detector (FID) detectoragainst the n-nonane internal standard. One ethylene oligomerization(Example 11) is performed in the absence of added Fe(acac)₂ and a secondethylene oligomerization (Example 12) is performed using a 10:1 molarratio of Fe(acac)₂ to PhenIFe 1. The ethylene oligomerization performedwith 10:1 molar ratio of Fe(acac)₂ to PhenIFe 1 produces an oligomerproduct which has productivity (in g (C₄-C₂₀)/mmol PhenIFe 1) 20%greater than the productivity of the ethylene oligomerization performedwithout added Fe(acac)₂.

Examples 13-15

The heteroatomic ligand iron dichloride2-[(2,6-diethylphenylimine)methyl-1,10-phenanthroline (PhenI 1) isprepared using the procedures disclosed in CN 104418690 A.

In a nitrogen-filled drybox, a stock cyclohexane solution of 0.13 mg/mL(3.65×10⁻³ meq/mL) of PhenI 1 and a stock cyclohexane solution 1.0 mg/mL(3.94×10⁻³ meq/mL) of Fe(acac)₂ are prepared. The appropriate amount ofthe PhenI 1 and the Fe(acac)₂ stock solutions are added to a 5 mL NMRtube to provide the desired quantity of PhenI 1 and of Fe(acac)₂ for theethylene oligomerization. The NMR tube is then sealed. Also in thenitrogen-filled drybox, a glass charger is charged with 200 mLcyclohexane, approximately 1.0 g of n-nonane internal standard, and theappropriate amount of MMAO-7 (Akzo Nobel, 7.0 wt % Al) to achieve thedesired α-diimine ligand to aluminum molar ratio for the ethyleneoligomerization. The glass charger is then sealed. The NMR tube andglass charger are then removed from the drybox. The NMR tube is securedto the stirrer shaft of a 1000 mL autoclave reactor with wire in amanner where the glass will shatter on starting the mixer. The autoclavereactor is then sealed and evacuated under high vacuum. The glasscharger is then affixed to a charging port on the top of the autoclavereactor. After evacuating the reactor for several minutes, the entirecontents of the glass charger are loaded into the autoclave reactorunder vacuum. The autoclave reactor is then degassed with ethylene bycarrying out several fill/vent cycles. The reactor is then pressurizedwith ethylene to 400 psig (2.8 MPa). Stirring is initiated resulting inbreakage of the 5 mm NMR tube and activation of the catalyst. Ethyleneis then fed to the autoclave reactor on demand to maintain a pressure of400 psig (2.8 MPa) for the remainder of the reaction. The reactiontemperature is maintained at a temperature of 60 to 70° C. by way ofcooling water passed through internal cooling coils inside the autoclavereactor. After 15 min, the reactor is cooled to room temperature andvented to atmospheric pressure. The liquid products are analyzed by agas chromatograph with a flame ionization detector (FID) detectoragainst the n-nonane internal standard. The first ethyleneoligomerization (Example 13) is performed with a 1:1 Fe(acac)₂ to PhenI1 molar ratio. The second ethylene oligomerization (Example 14) isperformed with a 5:1 Fe(acac)₂ to PhenI 1 molar ratio. The thirdethylene oligomerization (Example 15) is performed with a 10:1 Fe(acac)₂to PhenI 1 molar ratio. The ethylene oligomerization performed with 5:1molar ratio of Fe(acac)₂ to PhenI 1 produces an oligomer product whichhas productivity (in g (C₄-C₂₀)/mmol PhenI 1) over 400% greater than theproductivity of the ethylene oligomerization performed with a 1:1 molarratio of Fe(acac)₂ to PhenI 1. The ethylene oligomerization performedwith 10:1 molar ratio of Fe(acac)₂ to PhenI 1 produces an oligomerproduct which has productivity (in g (C₄-C₂₀)/mmol PhenI 1) over 600%greater than the productivity of the ethylene oligomerization performedwith a 1:1 molar ratio of Fe(acac)₂ to PhenI 1.

We claim:
 1. A process for forming an oligomer product comprising: a)introducing into a reaction zone i. ethylene; ii. a heteroatomic ligandmetal salt complex comprising a heteroatomic ligand complexed to a firstmetal salt where the first metal salt is an iron salt, a cobalt salt, ora combination thereof; iii. a second metal salt wherein an equivalentmolar ratio of the second metal salt to the heteroatomic ligand of theheteroatomic ligand metal salt complex is at least 0.5:1 and wherein thesecond metal salt has the formula MX_(n), where M is iron, cobalt, orany combination thereof, X represents a monoanionic species, and nrepresents the number of monoanionic species and has a value of 1, 2, or3; iv. an organoaluminum compound; v. optionally hydrogen; and vi.optionally an organic reaction medium; and b) forming an oligomerproduct in the reaction zone.
 2. The process of claim 1, wherein theorgano groups of the organoaluminum compound are substantially devoid ofβ,γ-branched organo groups and/or β,δ-branched organo groups.
 3. Theprocess of claim 1, wherein a C₄-C₂₀ productivity of the process is atleast 10% greater than the C₄-C₂₀ productivity of an otherwise similarprocess wherein an equivalent molar ratio of the second metal salt tothe heteroatomic ligand of the heteroatomic ligand metal salt complex isless than 0.1:1.
 4. The process of claim 1, wherein the heteroatomicligand of the heteroatomic ligand metal salt complex comprises 1) abidentate metal salt complexing moiety, or 2) a tridentate metal saltcomplexing moiety, wherein the bidentate metal salt complexing moietyand the tridentate metal salt complexing moiety each independentlycomprise at least two metal salt complexing groups selected from thegroup consisting of an imine group and an aromatic nitrogen atomcontaining group.
 5. The process of claim 1, wherein the heteroatomicligand of the heteroatomic ligand metal salt complex is an α-diimine, apyridine bisimine, a phenanthroline imine, or any combination thereof.6. The process of claim 5, wherein the heteroatomic ligand of theheteroatomic ligand metal salt complex is the α-diimine and theα-diimine comprises i) an α-diimine group, ii) a first imine groupconsisting of a hydrocarbyl group or a substituted hydrocarbyl groupattached to a first imine nitrogen atom of the α-diimine group, and iii)a second imine group comprising a first metal salt complexing group anda linking group linking the first metal salt complexing group to asecond imine nitrogen atom of the α-diimine group.
 7. The process ofclaim 6, wherein the α-diimine comprises i) an α-diimine group derivedfrom acenaphthenequinone, phenanthrenequinone, or pyrenequinone, ii) afirst imine group consisting of a 2,6-dihydrocarbylphenyl group attachedto the first imine nitrogen atom of the α-diimine group, and iii) asecond imine group comprising a diphenylphosphinyl first metal saltcomplexing group or a di(substituted phenyl)phosphinyl first metal saltcomplexing group and a —CH₂CH₂— linking group linking the first metalsalt complexing group to the second imine nitrogen atom of the α-diiminegroup.
 8. The process of claim 5, wherein the heteroatomic ligand of theheteroatomic ligand metal salt complex is the pyridine bisimine and thepyridine bisimine comprises i) a 2,6-bis[(arylimine)hydrocarbyl]pyridinewherein the aryl groups can be the same or different, ii) abis[(substituted arylimine)hydrocarbyl]pyridine wherein the substitutedaryl groups can be the same or different, or iii) an[(arylimine)hydrocarbyl],[(substituted arylimine)hydrocarbyl]pyridine.9. The process of claim 8, wherein the pyridine bisimine is selectedfrom the group consisting of 2,6-bis[(phenylimine) methyl]pyridine,2,6-bis[(2-methylphenylimine)methyl]pyridine,2,6-bis[(2-ethylphenylimine)methylpyridine,2,6-bis[(2-isopropylphenylimine)methyl]pyridine,2,6-bis[(2,4-dimethylphenylimine)methyl]pyridine,2,6-bis[(2,6-diethylphenylimine)methyl]pyridine,2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-methylphenylimine)methyl)pyridine,2-[(2,4,6-trimethylphenylimine)methyl]-6-[(3,5-dimethylphenylimine)methyl]pyridine,and2-[(2,4,6-trimethylphenylimine)methyl]-6-[(4-t-butylphenylimine)methyl]pyridine.10. The process of claim 5, wherein the heteroatomic ligand of theheteroatomic ligand metal salt complex is the phenanthroline imine andthe phenanthroline imine comprises a2-(hydrocarbylimine)-1,10-phenanthroline, a2-[(hydrocarbylimine)hydrocarbyl]-1,10-phenanthroline, a2-(arylimine)-1,10-phenanthroline, a2-[(arylimine)hydrocarbyl]-1,10-phenanthroline, a 2-(substitutedarylimine)-1,10-phenanthroline, or a 2-[(substitutedarylimine)hydrocarbyl]-1,10-phenanthroline.
 11. The process of claim 10,wherein the phenanthroline imine comprises a2-(2,6-dialkylphenylimine)-1,10-phenanthroline, a2-[(2,6-dialkylphenylimine)alkyl]-1,10-phenanthroline, a2-[(2,6-dialkylphenylimine)phenyl]-1,10-phenanthroline, a2-(2,4,6-trialkylphenylimine)-1,10-phenanthroline, a2-[(2,4,6-trialkylphenylimine)alkyl]-1,10-phenanthroline, a2-[(2,4,6-trialkylphenylimine)phenyl-1,10-phenanthroline, a2-(2,6-dihalophenylimine)-1,10-phenanthroline, a2-[(2,6-dihalophenylimine)alkyl]-1,10-phenanthroline, a2-[(2,6-dihalophenylimine)phenyl]-1,10-phenanthroline, or anycombination thereof.
 12. The process of claim 1, wherein theorganoaluminum compound comprises an aluminoxane.
 13. The process ofclaim 12, wherein the aluminoxane comprises methylaluminoxane, amodified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, sec-butylaluminoxane,iso-butylaluminoxane, t-butyl aluminoxane, 1-pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, iso-pentylaluminoxane,neopentylaluminoxane, or mixtures thereof.
 14. The process of claim 1,where the first metal salt comprises an iron halide, an ironβ-diketonate, an iron carboxylate, or any combination thereof and thesecond metal salt comprises an iron halide, an iron β-diketonate, aniron carboxylate, or any combination thereof and where the first metalsalt and the second metal salt are the same or different.